Review

pubs.acs.org/CR

Atomically Precise Clusters of Noble Metals: Emerging Link between

Atoms and Nanoparticles
Indranath Chakraborty† and Thalappil Pradeep*
DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology
Madras, Chennai 600036, India
*
S Supporting Information

ABSTRACT: Atomically precise pieces of matter of nanometer dimensions composed of

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noble metals are new categories of materials with many unusual properties. Over 100
molecules of this kind with formulas such as Au25(SR)18, Au38(SR)24, and Au102(SR)44 as
well as Ag25(SR)18, Ag29(S2R)12, and Ag44(SR)30 (often with a few counterions to
compensate charges) are known now. They can be made reproducibly with robust
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synthetic protocols, resulting in colored solutions, yielding powders or diffractable crystals.

They are distinctly different from nanoparticles in their spectroscopic properties such as
optical absorption and emission, showing well-defined features, just like molecules. They
show isotopically resolved molecular ion peaks in mass spectra and provide diverse
information when examined through multiple instrumental methods. Most important of
these properties is luminescence, often in the visible−near-infrared window, useful in
biological applications. Luminescence in the visible region, especially by clusters protected
with proteins, with a large Stokes shift, has been used for various sensing applications,
down to a few tens of molecules/ions, in air and water. Catalytic properties of clusters, especially oxidation of organic substrates,
have been examined. Materials science of these systems presents numerous possibilities and is fast evolving. Computational
insights have given reasons for their stability and unusual properties. The molecular nature of these materials is unequivocally
manifested in a few recent studies such as intercluster reactions forming precise clusters. These systems manifest properties of the
core, of the ligand shell, as well as that of the integrated system. They are better described as protected molecules or aspicules,
where aspis means shield and cules refers to molecules, implying that they are “shielded molecules”. In order to understand their
diverse properties, a nomenclature has been introduced with which it is possible to draw their structures with positional labels on
paper, with some training. Research in this area is captured here, based on the publications available up to December 2016.

CONTENTS 3.3.1. Advanced Mass Spectrometry 8219

3.3.2. MS/MS and Related Studies 8220
1. Introduction 8209 3.3.3. Single Crystal Studies 8222
1.1. Noble Metal Nanoparticles: From Alchemy 3.3.4. NMR Spectroscopy 8224
to Today 8210 3.3.5. Other Spectroscopies 8224
1.2. Gas Phase Clusters 8211 3.4. Other Gold Clusters 8225
1.3. Early Monolayer Protected Clusters: Au13 4. Atomically Precise Silver Clusters 8225
and Others 8212 4.1. Early Synthesis of Silver Clusters 8225
1.4. Brust Synthesis and Beyond: Monolayer 4.2. New Routes for Silver Clusters 8226
Protected Nanoparticles 8213 4.3. Well-Defined Mass Spectral Characterization 8226
1.5. Evolution of New Synthetic Methods at the 4.4. Single Crystal Studies 8228
Ultrasmall Regime 8213 4.5. Thermal Stability of Silver Clusters 8230
2. Monolayer Protected Clusters 8214 4.6. Emergence of Metallicity in Silver Clusters 8231
2.1. Entry of Mass Spectrometry to Noble Metal 5. Chemistry of Clusters 8231
Nanoparticles and Identification of Clusters 8214 5.1. Ligand Exchange 8231
2.2. Other Molecular Tools 8215 5.2. Ligand Conjugation 8233
3. Toward Atomic Precision: Gold Clusters 8216 5.3. Intercluster Reactions 8233
3.1. Synthesis and Separation of Au 25 (SR) 18 6. Alloy Clusters 8233
Cluster 8216 7. Protein Protected Clusters 8234
3.2. Evolution of the Electronic Structure 8217 8. Other Properties 8234
3.2.1. Optical Spectroscopy 8217
3.2.2. Photoluminescence 8218
3.3. Understanding the Composition, Structure, Received: November 12, 2016
and Properties 8218 Published: June 6, 2017

© 2017 American Chemical Society 8208 DOI: 10.1021/acs.chemrev.6b00769

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8.1. Two-Photon Absorption 8234 superatom model8−10 which is based on the “jellium” model
8.2. Magnetism 8236 of electrons confined within a spherically symmetric potential
9. Applications 8236 well of the metal core. If the number of free electrons falls in
9.1. Sensors 8236 the “magic” number series of 2, 8, 18, 20, 34, 58, ..., the cluster
9.2. Biological Applications 8238 shows high stability.8−10 The number of free electrons of a
9.2.1. Biolabels 8238 metal cluster protected with ligands (such as thiolate) is
9.2.2. Biomedical Targeting 8239 calculated as Ns = NvA − L − q, where Ns is the shell closing
9.2.3. Other Biological Applications 8239 number (free electron count), N is the number of core metal
9.3. SERS 8239 atoms, vA is the effective valence electrons (for Au/Ag, vA = 1),
9.4. Catalysis 8240 L is the number of one-electron withdrawing ligands, and q is
9.5. Solar Cells 8240 the total charge (+q or −q) on the cluster.10 Ligands such as
10. New Materials 8242 phosphine or amine do not withdraw electrons; rather they
10.1. Graphene Composites 8242 bond to a metal core through a dative bond and do not get
10.2. Other Composites 8242 counted in the way they are counted in Ns.
11. Optical Chirality 8244 Assigning an appropriate name to these atomically precise
12. Similar Structures 8244 pieces of matter has been a challenge, and they have been
12.1. Hydride-Rich Silver Clusters 8244 referred to variedly, such as nanoparticles, quantum dots,
12.2. Silver Sulfide Clusters 8246 clusters, nanoclusters, quantum clusters (QCs), monolayer
13. Atomically Precise Pt and Pd Clusters 8246 protected clusters (MPCs), nanomolecules, artificial atoms,
13.1. Platinum Clusters 8246 superatoms, faradaurates, etc. However, this class of materials
13.2. Palladium Clusters 8247 has molecule-like optical properties, so it is not appropriate to
14. Naming and Structural Understanding 8248 treat them as nanoparticles, which exhibit distinctly different
15. Future Prospects 8248 optical features.7 Many of the emerging chemical phenomena of
15.1. New Synthetic Methodologies 8248 these materials emphasize their molecular nature. “Nano-
15.2. Ligand Induced Properties 8248 clusters” and “quantum clusters” are more suitable titles as such
15.3. Alloys 8248 atomically precise pieces have quantized energy levels and, as a
15.4. Hydride-Rich Clusters 8249 result, show multiple bands in their optical spectra, resembling
15.5. Cluster Composites 8249 molecules. Thus, naming them continues to be an issue. We
15.6. Computational Approaches 8249 will revisit this topic later in the text.
15.7. Stabilizing Cluster Luminescence 8249 Tens of such nanoclusters are now known with detailed mass
15.8. Crystallization 8249 spectral data,11,16,27−37 and among them a few have also been
15.9. Intercluster Reactions 8249 characterized with single crystal X-ray diffraction.15,38−47 With
15.10. Cluster Assembled Solids 8249 new preparation methods48 and adaptation of modern
15.11. Clusters as New Molecules 8249 separation methodologies, synthesis of a large number of
Associated Content 8250 unique materials in the immediate future is highly possible. The
Supporting Information 8250 possibility to create well-defined clusters with different ligands
Author Information 8250 and associated variation in chemical properties has led to a
Corresponding Author 8250 plethora of applications ranging from chemistry to biology and
ORCID 8250 also from materials science to devices.49−53 An illustration of
Present Address 8250 these clusters and their diverse possibilities is presented in
Notes 8250 Figure 1.
Biographies 8250 Combining properties of other nanosystems, such as
Acknowledgments 8250 graphene, with clusters has resulted in novel composites.54
Abbreviations 8250 Creation of atomically precise clusters in proteins and
References 8250 biomolecular templates has given other directions in chemical
Note Added in Proof 8271 research.55 Utilizing the unique chemistry of these systems, new
sensors have been developed and extension of this science has
created new materials for contaminant removal from surface
1. INTRODUCTION waters.56 Modification of electronic structure in the cluster size
Electronic confinement in nanoscale pieces of matter of noble regime has been used in catalysis, which has given rise to
metals has resulted in giant advances in science and unusually large conversion efficiencies for several trans-
technology.1 Chemical synthesis of such materials,2 manipu- formations. Modification of the metal core itself has produced
lation of their properties, and utilization of emerging novel alloys with precise composition and systematic variation
phenomena at this length scale have all contributed to this in properties. Electronic structures of these systems can be
advancement.3,4 As dimensions of such particles shrink further, controlled by ligands that can also induce chirality in the overall
novel molecular properties evolve in the cluster regime of system. The cluster core itself can be chiral, and such chiral
materials, especially in metals. Such atomically precise entities induction depends on various parameters. Studies in this area
are composed of a few to tens of atoms of metals with a definite have greatly benefited by the use of advanced instrumentation,
ligand shell, forming molecules of definite composition.5−7 For especially adaptation of soft ionization mass spectrometry.
the purpose of this review, we considered only those particles Understanding of these structures, reasons for their increased
with precise formulas possessing optical properties, which are stability and chemical reactivity including catalysis, assignments
different from corresponding plasmonic nanoparticles. Their of their electronic transitions, and predictions of their emerging
stability in electronic terms has been explained by the properties have immensely benefited from the advances in
8209 DOI: 10.1021/acs.chemrev.6b00769
Chem. Rev. 2017, 117, 8208−8271
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Figure 1. Illustration of monolayer protected clusters, their chemical diversity, and different studies performed using them. Parts of the images are
from the literature.11−26

computational materials science. A schematic diagram of the treatments.92 Egyptians used gold for physical, mental, and
evolution of such clusters over the years is provided in Figure 2. spiritual purification.92 In Ayurveda (an Indian medical
Research in this area extending over 5000 research publications system), gold has been used in several preparations; one such
(Figure 2, inset) suggests an explosion of activities in the near example is Saraswatharishtam, usually prescribed for memory
future, and a consolidated documentation is necessary at this enhancement. The chemical synthesis of colloidal gold particles
stage. It is important to mention that since there was a recent was discovered by Michael Faraday in 1857.93 He observed the
review article7 covering theoretical aspects of clusters, our focus formation of deep red colored colloidal gold when aqueous
is only on experimental research. solution of AuCl4− was reduced by phosphorus in carbon
1.1. Noble Metal Nanoparticles: From Alchemy to Today disulfide (CS2).
Similar to gold, silver also has a historical background. The
“Noble metals” refers to those metals that are resistant to
color of the Lycurgus Cup is due to Au−Ag nanoparticles. But
processes such as oxidation under normal atmosphere. They are
the major use of silver in those days was in medicinal field,
ruthenium, rhodium, osmium, iridium, palladium, platinum,
silver, and gold. Because of their poor abundance, all of them mainly as an antimicrobial agent. Silver vessels were used to
are also precious, to varying degrees. Among the noble metal keep water fresh by Greeks.92 But they were not aware of the
nanoparticles,57−86 those of gold and silver have drawn antibacterial properties of silver. The purpose of addition of
tremendous interest from the scientific community because of silver was to increase the clarity, reduce odor, and improve the
their versatile applications.87−90 Starting from historical times, taste of water. The Greeks may have understood that disease-
gold and silver have been used extensively by mankind for causing pathogens would not survive in the presence of silver,
several purposes including coloration of glass, as well as in and perhaps for that reason silver was used in drinking vessels,
esthetic and medicinal practices. A mixture of gold salts with dishware, and eating utensils, although microbes as disease-
molten glass was used to produce gold colloids of rich ruby causing agents was suggested only in 1880.94 Even in other
color. In the medieval days, artisans exploited many such medical therapies such as bone prostheses, ophthalmic surgery,
varieties for the coloration of ceramics and glasses. The oldest etc., silver was used extensively. Silver colloids were made by
example of these is the fourth century A.D. Lycurgus Cup made Frens, Overbeek, and Lea in 1969 when they reduced silver
by the Romans. Purple of Cassius, a pink pigment commonly nitrate using ferrous sulfate in the presence of citrate ion which
used in the 17th century, was a combination of gold particles acted as a protecting agent.95 Scientists have shown huge
and tin dioxide.91 Using metallic minerals including gold, the interest thereafter in silver colloids and their antibacterial
great alchemist and the founder of modern medicine, properties.96−99 Until the last century, the use of gold and silver
Paracelsus (1493−1541), developed many highly successful particles was restricted only for medicinal and antibacterial
8210 DOI: 10.1021/acs.chemrev.6b00769
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Figure 2. Evolution of clusters (of the type described here) with respect to time. Inset shows the number of papers published and citations in each
year for metal nanoclusters (collected from Web of Science using “gold nanoclusters” or “silver nanoclusters” as keywords). The data were collected
up to Dec 31, 2016.

activity, but now it is being explored intensely in catalysis, noble metal clusters.102,104 The study of gas phase Au and Ag
optics, and several other biological applications.87,89,90,100,101 clusters was initiated in the 1960s.106,110 Chemical sputtering of
Even in the 15th and 16th centuries, people of Deruta used gold and silver metal targets by inert gas ions produced smaller
silver and copper nanoparticles to fabricate glazes. They mixed naked clusters.115 Coalescence of such clusters formed larger
copper and silver salts with vinegar, ochre, and clay and applied clusters.116 Such studies have also been done with pulsed laser
them on the surface of already glazed pottery for fabrication.92 evaporation.102 The clusters so formed exist as neutral or ionic
Therefore, from alchemy to today, noble metals such as gold (positive or negative) entities and have been detected by
and silver have been used for a large number of applications in various mass spectrometric techniques such as Wien filter, time-
several directions because of their diverse properties. A of-flight (TOF) analyzer, quadrupole mass filter (QMF), ion
historical account of the use of noble metals is provided in cyclotron resonance (ICR) spectrometer, etc.102 Katakuse et al.
ref 92. have investigated a series of copper (Cu)n+, silver (Ag)n+, and
1.2. Gas Phase Clusters gold (Au)n+ clusters up to the size n = 250.115 These clusters
were generated by bombardment of 10 keV Xe ions and
Clusters made in the gas phase have drawn tremendous interest analyzed using a sector-type mass spectrometer. Details of
from the scientific community,102 especially after the discovery several gas phase atomic and molecular clusters can be found in
of C60.103 For any material, the number of surface atoms is very the book of R. L. Johnston.117
important as it controls its properties. In a cluster (assumed to Baksi et al.118 have shown the existence of clusters such as
be spherically shaped), the fraction F of surface atoms is F = 4/ Au18+, Au25+, Au38+, and Au102+ with unprotected metal cores,
n1/3, where n is the total number of atoms. It can be seen that F having unusual stability in the gas phase. These clusters were
is equal to 0.3, 0.2, and 0.04 when n is 1000, 10 000 and prepared via laser desorption ionization of the precursor metal
1 000 000, respectively.102 Normally, in gas phase clusters, ions in protein templates. Nucleation occurred in the vicinity of
valencies of the surface atoms are unsatisfied, because of which the protein in the gas phase. In another report, using a similar
they are extremely reactive. For this reason, clusters cannot be approach, alloy clusters of the type Au24Pd+ were detected.119
kept in a free state and they should be made in situ, in Even though over the years many efforts have been made to
experimental apparatuses where the properties are to be improve the synthesis techniques of these clusters and to
investigated. That is why practically all the studies of such understand them in great detail, isolation of such gas phase
clusters are carried out in a vacuum or in inert (noble) gases.104 species continues to be a challenge and so far no reports exist in
Gas phase clusters are usually made through a variety of cluster the literature. Deposition of such gas phase clusters on
sources, such as laser vaporization source, laser ablation cluster substrates120−123 will open the field of cluster catalysis, as
source, pulsed arc cluster ion source, ion sputtering source, these systems are catalytically active.124 Much of such
liquid metal ion source, etc.102,104 The concepts of electron supported cluster catalysis research is documented in two
shell closing based on the jellium model105 and superatoms8 recent review articles.125,126 Lu et al. have reported the effect of
were established after the observation of such gas phase metal size-selected silver clusters on lithium peroxide batteries.127
clusters. They have deposited ultrasmall atomically precise silver clusters
Although there are numerous reports on gas phase clusters on passivated carbon to study the discharge process in lithium−
such as ionic, covalent, metallic, molecular, van der Waals, oxygen cells. Dramatically different morphologies of electro-
etc.,9,106−114 in the present context, we will focus mainly on chemically grown lithium peroxide were seen depending on the
8211 DOI: 10.1021/acs.chemrev.6b00769
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size of the clusters. Therefore, by controlling the surface

structure on cathodes, the performance of lithium−oxygen cells
can be improved.
1.3. Early Monolayer Protected Clusters: Au13 and Others
Gas phase clusters cannot be isolated in the free form as they
are not stable in ambient conditions. Using protecting ligands,
it is possible to synthesize nanoparticles or nanoclusters in the
solution phase. After the discovery of Faraday’s colloidal
particles, several efforts were made to synthesize colloids of
noble metals, but most of them resulted in nanoparticles with a
broad size distribution. Turkevich et al.128 have discovered a
simple way to synthesize colloidal gold in 1951 which was then
refined by Frens132 in the 1970s. In their method, gold chloride
was reduced by sodium citrate in aqueous medium.
Creation of highly monodisperse nanoparticles was a great
challenge in those early days. Phosphine type ligands were used
at that time to protect the gold core. The very first report of
Au11(SCN)3(PPh3)7133 came in 1969, which was followed by
the crystal structure of Au11I3[P(C6H4-p-Cl)3]7 in 1970.129 The
Au11 cluster can be best described in terms of an incomplete
icosahedron, where the central gold atom [Au(1)] is
surrounded by 10 other gold atoms as depicted in Figure 3a. Figure 3. (a) Crystal structures of Au11I3[P(C6H4-p-Cl)3]7 cluster
Other derivatives of Au11 also exist in the literature.134 Many (phosphine groups have been omitted for clarity). Only gold atoms are
clusters with lower nuclearity have also been reported.135−140 numbered, although not sequentially as all the atoms in the cluster
Clusters of very small nuclearity,135−138 such as Bertand’s including ligands are counted. Reprinted with permission from ref 129.
mono- and diatomic Au complexes141 and Schmidbaur’s Copyright 1970 Royal Society of Chemistry. (b) Molecular structure
of the [Au13(PPhMe2)10C12]3+ ion. For reasons of clarity, the carbon
tetraatomic Au complex,142 suggest that this class of materials and hydrogen atoms on the phosphine ligands have been omitted.
indeed bridges the gap between molecules and nanoparticles. Reprinted with permission from ref 130. Copyright 1981 Royal Society
The Au8(PPh3)7(NO3)2143 and Au9[P(C6H4-p-Me)3]8(PF6)3144 of Chemistry (c) Perspective view of the [Au9Ag4Cl4(PMePh)2]8+
clusters exist as incomplete icosahedrons, whereas cluster ion. Phosphine substituents and bonds to the central atom are
Au10Cl3(PCy2Ph)6NO3145 shows a D3h symmetry (many omitted for clarity. Key to atoms: gold, fine speckling; silver, course
more clusters are listed in Table S1). Several theoretical speckling; phosphorus, no pattern; chlorine, herringbone. Reprinted
analyses predicted the existence of higher nuclearity gold with permission from ref 131. Copyright 1996 Royal Society of
clusters such as Au13. In 1981, Briant et al. solved the crystal Chemistry. (d) Schematic view of the growth of shell structure of
structure of the Au13 cluster which has a perfect icosahedral clusters: Initially a single atom is surrounded by 12 other atoms to
form a 13 atom core−shell M13 cluster. Then, 42 atoms can be densely
structure (Figure 3b) with a central gold atom.130 Many groups packed on the surface of 12 atoms to produce a two-shell M55 cluster;
have studied this cluster extensively.146−151 [Au20(PP3)4]Cl4 in a similar fashion, a shell of 92 atoms can form over the second shell
(PP3, tris[2-(diphenylphosphino)ethyl]phosphine)152 and to generate a three-shell M147 cluster and this series may continue.
[Au39(PPh3)14Cl6]Cl2 have also been reported with phosphine
protection.153 Some alloy clusters such as
[Au9Ag4Cl4(PMePh)2]8+ (Figure 3c),131 [(p-
Tol3P)10Au13Ag12Br8](PF6),154 [(p-Tol3P)12Au18Ag20Cl14],155 simulation of STEM images, they predicted that 42% of the
and [Au12Ag12M(PR3)10Cl7]+ (M = Pt, Ni)156 have also been clusters present on the TEM grid possess a hybrid structure
reported. The [(p-Tol3P)10Au13Ag12Br8](PF6) cluster is con- (composed of icosahedral, cuboctahedral, and ino-decahedral
structed by two icosahedrons sharing a vortex atom (later, a shapes) and the remaining 58% are amorphous in nature. These
similar structure was seen for a rod-shaped Au25 cluster with reports suggest that the Schmid synthetic route176 does
phosphine and thiol protection47). In 1981 Schmid et al.157 produce the Au55(PPh3)12Cl6 cluster along with a few other
reported a 55 atom cluster, Au55(PPh3)12Cl6, which has a high clusters, composed of 35−60 Au atoms.
tendency to self-assemble forming one- (1D),158,159 two- The most interesting aspect of clusters such as Au13 or Au55
(2D),160 and three-dimensional (3D)161 organized structures. is the unique full shell structures which explain their stability.
Because of this self-organization, Au55 cluster has been used in The expression “full shell cluster” refers to a particle composed
several applications.162−168 Single crystal studies and proper of a central atom that is surrounded by individual shells of
mass spectral characterization of this particle have not been atoms, eventually resulting in perfect geometries. The
reported yet, which makes the existence of this species icosahedral geometry is a perfect example of this kind. The
controversial. However, the formation of Au55 core has been general rule for construction of such clusters is the number of
proven by mass-spectrometric analysis of thiolated Au55 atoms in the cluster = 1+ ∑(10n2 + 2), where the summation
analogues.34,169,170 Several microscopic studies have shown runs over all the shell numbers (n = 1, 2, ...) in the cluster. A
the structural details of Au55 and its monodispersity.171−173 schematic is given in Figure 3d to understand the formation of
Recently, the Palmer group has probed the structure of such shells. Au13 cluster (n = 1) has been described as a one-
Schmid’s Au55 cluster, using direct atomic imaging techni- shell cluster where a central atom is coordinated to the
ques.174,175 Based on aberration-corrected scanning trans- remaining 12 atoms which form the first shell. More details
mission electron microscopy (STEM) combined with multislice about the phosphinated gold clusters can be found in Table S1.
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1.4. Brust Synthesis and Beyond: Monolayer Protected Nanoclusters of different sizes and of different noble metals
Nanoparticles (Au, Ag, Pd, etc.) can be synthesized easily using this
Two different approaches, namely bottom up and top down, method.170,179−182
have been followed to synthesize noble metal nanoclusters. Among the monolayer protected metal nanoclusters, gold
In the bottom-up approach, nanoclusters are synthesized has been studied extensively because of its high stability under
from metal ion precursors by reducing them in the presence of ambient conditions. From the early reports, it was believed that,
suitable ligands. It is the most efficient way to nucleate clusters, in the Brust protocol, an [Au(I)SR]n polymeric compound is
and most importantly, nucleation can be controlled by varying formed during the reduction of Au(III) to Au(I) in the
the quantities of the ligands and reducing agents or by varying presence of alkanethiol (RSH). But recently, Goulet and
the solvents. Aqueous and organic soluble clusters can be Lennox183 have revised the view of the Brust method from an
produced using this approach. Synthesis of noble metal analysis of 1H NMR data. According to their suggestion, in a
nanoclusters got a new direction after the easy and effective one-phase method, Au(I)thiolate is likely to be the precursor,
method developed by Brust et al.177 in 1994. The Brust method but for the two-phase Brust method, Au(I)−tetraoctylammo-
is an example of the bottom-up approach to synthesize organic nium halide complex [TOA][MX2] is the main precursor rather
soluble metal nanoparticles as well as nanoclusters. The than the [Au(I)SR]n polymers before the reduction. The same
procedure followed a two-phase synthetic protocol in which was suggested by Li et al.184 through their detailed Raman and
water and an organic nonpolar solvent (mainly, toluene) were NMR analyses. These revised views help understand the
used as the two phases. The metal precursors were first mechanism of this method.
dissolved in an aqueous solution and then phase transferred to In one-phase Brust−Schiffrin method, a polar solvent such as
the organic solvent using phase transfer reagents such as methanol or THF was used as solvent. Several modifications of
tetraoctylammonium bromide. Finally, organic protecting this method have appeared, mainly by controlling different
ligands and reducing agents were added to the mixture to parameters such as temperature, solvents, concentration of each
obtain nanoclusters. Perala and Kumar178 have tried to explain reactant, reducing agents, etc., to get highly monodispersed
the mechanism of this method. According to them, phase nanoclusters. Zhu et al. have synthesized Au25(SR)18 cluster just
transfer of chloroauric acid to the organic phase in the presence by tuning the stirring rate and controlling the temperature.185
of the phase transfer catalyst (PTC) occurs through the Wu et al. have introduced a facile single-phase (using THF)
following equation: method to synthesize Au25(SR)18 cluster by “size focusing”.186
For water-soluble gold clusters, metal ions are first reduced to
H+AuCl4 −(aq) + (R 8)4 N+Br−(toluene) Au(I) complex by water-soluble ligands which is followed by
reduction using suitable reducing agents. In most of the cases,
= (R 8)4 N+AuX4 −(toluene) + HX(aq) (1) sodium borohydride (NaBH4) has been used as the reducing
Since the extent of substitution of Cl− by Br− is not known, agent.187
X represents both Cl and Br. Then the reduction of Au(III) to In the top-down approach, the nanoclusters are synthesized
Au(I) by thiol was believed to occur through the following from bigger nanoparticles by either core etching or size
equation: reduction. Initially, a metal nanoparticle is synthesized which is
then treated with extra ligands or metal ions to form
(R 8)4 N+AuX4 −(toluene) + 3RSH → −(AuSR)n − nanoclusters. Duan and Nie 188 in 2007 showed that
polyethylenimine (PEI), a first generation dendrimer, could
+ RSSR + (R 8)4 N+ + 4X− + 3H+ (2) be used to synthesize nanoclusters from dodecylamine capped
organic soluble metal nanoparticles. The synthesized cluster
At this stage, it was believed that the toluene phase contains was identified as Au8 from electrospray analysis, and the cluster
PTC, dialkyl sulfide, Au(I)SR polymer (n is the number of was found to be highly luminescent. Qian et al.189 in 2009
AuSR monomers) and AuX4−, either complexed with PTC synthesized Au25 nanorods and nanospheres from polydis-
cation or excess RSH depending on the ratio of the ingredients. persed phosphine protected nanoparticles through a thiol
In the final step, the reduction of Au3+ or Au+ to Au0 happens etching procedure. As mentioned above, along with ligands,
by borohydride according to the following equation. metal ions have also been used as etching agents. Lin et al.190
have shown that, when didodecyldimethylammonium bromide
−(AuSR)n − + BH4 − + RSH + RSSR → Aux (SR)y (3) (DDAB) stabilized nanoparticles were treated with Au
precursors (HAuCl4 or AuCl3), a transparent solution was
(R 8)4 N+AuX4 − + BH4 − + RSH + RSSR → Aux (SR)y formed. A subsequent phase transfer and ligand exchange by
(4) dihydrolipoic acid (DHLA) resulted in the formation of red
luminescent gold clusters.
Now, for the cluster case, depending on the ratio of Au, thiol,
1.5. Evolution of New Synthetic Methods at the Ultrasmall
and sodium borohydride, the x and y values change (please
Regime
note that reactions 2, 3, and 4 are not balanced reactions;
impurities such as other clusters or some thiolates are also Apart from this traditional solution phase synthesis, several new
present in the final product for reactions 3 and 4, which were protocols such as interfacial synthesis,14,191 carbon monoxide
generally removed during the purification step). In most of the (CO) directed method,192 solid-state route,16,36,37,193−196 etc.,
cases, some Au(SR) polymer remains as staple motifs such as have been proposed lately as alternative approaches to
Au2(SR)3 or Au(SR)2 in the cluster structure, which suggests synthesize atomically precise nanoclusters. A perspective article
that they get restructured during the cluster growth and only by Udayabhaskararao and Pradeep48 summarizes the advance-
the remaining gold species are reduced to the zero oxidation ments in the synthesis of noble metal nanoclusters. A brief
state. synopsis of all the synthetic routes is presented in Table 1.
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Table 1. Different Routes Used for the Synthesis of Nanoclusters

method
example ref
top down alloying (CunAu25−n)SR18 (n = 1−5), Au24Pd(SR)18, Au24Pt(SR)18, 17, 197−199
Ag7Au6(H2MSA)10
etching ligand induced Au25(SG)18 200
temperature induced Ag@MSA and Au@DT 201, 202
other Ag7(H2MSA)7 and Ag8(H2MSA)8 14
ligand exchange Au24Pd(DDT18−nSBBn), Au25(DDT18−nSBBn) 12
bottom up Brust method Au25(SC6H13)18, Au55(SC18)32 34, 180
modified Brust method Au38(SC12H25)24, Au38(PET)24 203, 204
photoreduction Ag@SG, Ag@PAMAM 21, 205
microwave assisted Ag@L-SG 206
radiolytic approach Ag32+ and Ag42+ 207, 208
microemulsion AgnQCs 209
technique
sonochemical synthesis Ag@PMAA 210
electrochemical Cu@TBAN 211
synthesis
template mediated thiols and amines Au25SG18, Ag∼4,5@DHLA 200, 212
proteins Ag15@BSA, Au25@BSA, Au@NLF 32, 213, 214
polymers Ag@LA-PEG 215
gels Ag25@SG 216
DNA Ag@DNA 217
dendrimers Ag@PAMAM 210
solid state route Ag9, Ag44, Ag55, Ag152, Pt11, Cu@PET 16, 36, 37, 193, 195, 218
high temperature route ∼Ag75(SG)40 11
slow reduction method Au18(SG)14 219
other solution phase Ag44(4-FTP)30, Ag44(MBA)30, Ag44(SePh)30, Ag5Pd4(SePh)12 30, 44, 196, 220−222

Box 1. Important Pointers in Monolayer Protected 2. MONOLAYER PROTECTED CLUSTERS

Nanoclusters Synthesis and characterization of monolayer protected gold
clusters has become one of the prime interests of materials
Some of the landmarks in the science of these materials are chemists. Although there have been several reports on
listed as follows: 1969−1981: Synthesis of cluster compounds phosphine protected gold clusters, very few reports existed
such as Au11133 and Au13130 occurred. 1994: Brust−Schiffrin with thiol protection in the early days of these materials
developed two-phase methods for the synthesis of monolayer (1990−2000s). In the following sections, we will mainly discuss
protected gold nanoparticles.177 1996: Whetten group ex- the thiol protected clusters which have been synthesized and
plored the gold nanocrystal’s core sizes by laser desorption characterized during this period.
mass spectrometry. 223 1997: Cleveland and Landman
developed a structural model for gold clusters.224−226 1997− 2.1. Entry of Mass Spectrometry to Noble Metal
Nanoparticles and Identification of Clusters
2000: Whetten and Murray groups started exploring the gold
cluster chemistry.227,228 2005: Tsukuda group identified Emergence of mass spectrometry (MS) as a principal tool of
Au25SG18 through mass spectrometry.229 2005: Kimura characterization of monolayer protected clusters is largely due
group made enantiomers of nanoclusters.230 2006: Hakkinen to the versatility of soft ionization tools. Ionization of clusters
developed the “divide and protect’’ concept.231 2007: directly from solution and from solid state by electrospray
Jadzinsky et al. reported the first crystal structure of ionization and matrix assisted laser desorption ionization
Au102(SR)40. 2008:45 Murray and Jin groups reported the (LDI), respectively, have increased the power of mass
crystal structure of Au25(SR)18.15,41 2009: Ying group spectrometry. Coupled with the capability to do analysis of
synthesized a highly fluorescent protein protected gold extended mass ranges and additional capabilities such as
cluster.213 2009−2010: Many synthetic routes were used to fragmentation, mobility separation, and surface induced
make clusters such as the “solid state route”37 to synthesize dissociation, MS can provide more information. Mass
silver clusters. 2013: Bigioni and Zheng groups determined the resolution has also changed tremendously in the recent past
crystal structure of Ag44(SR)30.44,222 2015: Bakr group found with new instrumentation touching numbers of the order of
the crystal structure of Ag25(SR)18.46 2015: Pradeep group 50 000 (m/Δm). This makes it possible to assign mass peaks to
developed a nomenclature for clusters.232 2016: Cluster unique products in view of the specific isotope patterns of
chemistry was being developed; clusters react in solution various entities.
between each other, conserving the structural motif, just like MS played an important role in identifying and under-
molecules.233 standing gas phase clusters. Fullerene family is the classic
example here which includes C60 and C70.103 Several metals
such as alkali, alkaline earth, and transition metals have been
studied in the gas phase.234−236 In most of the cases, a
discontinuous variation in intensity at N = 2, 8, 20, ..., 92 atoms
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Figure 4. (a) Scheme of Au@SG cluster synthesis. (b) The PAGE shows nine isolated bands that were subsequently extracted in water.
Corresponding photographs of all the cluster solutions are shown in (c). Reprinted from ref 229. Copyright 2005 American Chemical Society. (d)
Photographs of the reaction mixture at different times during the synthesis of Au25(Cys)18 in the presence of CO. Inset shows the UV/vis spectrum
of Au25(Cys)18 cluster. Reprinted from ref 192. Copyright 2012 American Chemical Society.

has been observed, which might be because of the high stability 2.2. Other Molecular Tools
of these clusters.235 Silver clusters with odd numbers of atoms Other than mass spectrometry, several new molecular tools to
are more intense as compared to clusters with even numbers of characterize these clusters in more detail have been introduced
atoms. The former (2, 8, 20, ...) has an even number of valence by several research groups. Because of their distinct optical
electrons which results in spin pairing, and this enhances their properties and photoluminescent nature, scientists started
stability as opposed to the latter which has an odd number of looking at these particles as molecules. Thus, optical spectros-
valence electrons.115,237 Several molecular clusters have also copy became the immediate tool to understand the electronic
been studied intensely by mass spectrometry.238,239 structure of these clusters.223,227,241,243,248 This investigation
Along with gas phase clusters, mass spectrometry has given was also influenced by the fact that optical absorption
important directions to analyze noble metal cluster systems, spectroscopy is one of the most important methods for
prepared in solution.240 The Whetten and Murray groups characterizing plasmonic nanoparticles. Distinct differences
initiated early studies to identify such clusters using mass between these two categories of nanosystems are clear from
spectrometry and o ther characterization techni- such investigations. We will come back to this topic later in the
ques.223,227,241−243 Whetten et al.223 showed a series of clusters text. Fluorescence spectroscopy has provided a new direction to
with molecular mass starting from 27 to 93 kDa in thiol the investigations which showed that these clusters can emit
protected Au clusters. Based on the core size from TEM from the visible to the near-infrared (NIR) region, depending
analysis and mass spectral characterization, they assigned on their core size.249,253 Energy gap between the highest
clusters to be composed of 140−459 gold atoms. LDI MS occupied and lowest unoccupied molecular orbitals (HOMO
was used mainly to identify the core mass. Clusters of core and LUMO) and other features of the electronic structure have
masses 5.6,227 14.0,244 22.0,244 28.0,241 29.0,244 and 66.0 kDa245 also been probed electrochemically using cyclic voltammetry
are known from their reports. In most of the cases, clusters (CV) or differential pulse voltammetry (DPV) experi-
were alkane (butane, hexane, octane, or dodecane) thiol ments.241,245−247 Along with characterization, isolation of
protected. The effect of chain length on cluster properties was such clusters is also important and polyacrylamide gel
also studied extensively by Whetten and colleagues.246 Some electrophoresis (PAGE) has been introduced for separating
reports on gold clusters protected with glutathione,244 clusters of different sizes.227,244,254 PAGE requires two kinds of
functionalized alkenethiols,228,247 or tiopronin245 are also gels: a stacking gel and a separating gel. Mostly acrylamide and
known. Among the clusters reported during those early years bis(acrylamide) have been used in different weight percentages
[1990s], only a few were tentatively assigned. The cluster of to create these gels. Normally, the sample solutions are loaded
core mass 29.0 kDa was suggested to have a composition of onto the stacking gel and then eluted for a long time at a
Au144−146(SR)50−60.248 Schaaff et al. assigned the 5.6 kDa (core constant voltage to get sufficient separation. The clusters are
mass) cluster as Au28(SG)18, and subsequently several reports separated based on their size and aqueous soluble clusters;
came from the same group on the same cluster.227,249 Later, especially ligands with carboxylate functionality work well for
Negishi et al.229 reassigned the cluster as Au25(SG)18 in 2005 PAGE separation. Separation can easily be observed by looking
which is now one of the most studied clusters. Similarly, at the gels with different colors which are then cut and
Murray’s initial reports of Au38(SR)24 clusters250−252 were later extracted in appropriate solvents to get the purified cluster. For
corrected as Au25(SR)18. Among the clusters reported so far, organic soluble clusters, chromatographic techniques such as
most of them have been assigned based on mass spectrometry, high performance liquid chromatography (HPLC),12,255,256 gel
either by electrospray ionization (ESI) or matrix-assisted laser permeation chromatography (GPC),170 size exclusion chroma-
desorption/ionization (MALDI) MS (Table S1). Detailed tography (SEC),257 and thin layer chromatography (TLC)258
discussion of these clusters is presented in section 3.3.1. work well. More details about a few important techniques along
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with their recent advancement have been mentioned in section size. They successfully isolated the 10.4 kDa cluster compound
3. which was initially assigned as Au28(SG)16 based on ESI MS
analysis. After that, Negishi et al.261 in their procedure reduced
3. TOWARD ATOMIC PRECISION: GOLD CLUSTERS the Au(I)−SG polymer in ice-cold condition which resulted in
a mixture of glutathione protected gold clusters (a schematic of
Starting from Faraday’s colloidal gold to particles synthesized
the process is illustrated in Figure 4a). Initially, six clusters were
through the Brust method, monodispersity has been improved
tremendously. While several examples of such clusters are Box 2. Synthesis of Au25(SR)18 Cluster
known today, it is not possible to discuss the synthesis of all of
them in great detail in this review. To illustrate the case of gold About 2 mL of 50 mM HAuCl4·3H2O in THF was diluted to
clusters and highlight their essential characterization, 7.5 mL using THF. About 65 mg of TOAB was added to this
Au25(SR)18 is considered as a representative system and a solution and stirred at 1500 rpm for 30 min at room
brief description is given below. temperature. The initial yellow color of the solution turned
3.1. Synthesis and Separation of Au25(SR)18 Cluster deep red during stirring. About 0.5 mmol of pure thiol was
added at a stretch while stirring at the same speed. The deep
Monolayer protected gold quantum clusters and the evolution
red color slowly turned to yellow and eventually became
of their electronic, optical, and chemical properties as a function
colorless after about 45 min. After stirring further for 2 h, 2.5
of the core size has led to new avenues in the field of cluster
mL of ice-cold aqueous NaBH4 (0.2 M) was added in one
chemistry.259 To develop the chemistry of these new
shot. The solution turned black immediately, and stirring was
nanosystems, there is indeed a need for novel procedures to
continued for 5−8 h depending on the ligands. A continuous
synthesize such classes of materials with high purity. Several
monitoring of the UV/vis spectra is needed. Once the Au25
attempts have been made to create highly monodisperse
cluster has formed, all features will be prominent and optical
particles of desired size (which are often treated as nanoclusters
spectra will not change over time. The solution was rotary
or nanomolecules) by optimizing the synthesis conditions such
evaporated and precipitated with methanol (∼4 mL), washed
as solvent, gold-to-thiol ratio, temperature, reducing agent,
repeatedly with the same, and dried (three times, until the
etc.260 Chemical reduction of Au(I) ions in the presence of
smell of thiol was completely gone). This gives the purified
thiols is the usual trend for synthesizing such clusters. The very
and dried Au25 cluster which can be stored in a refrigerator (4
first report of glutathione (SG) (a tripeptide composed of
°C). With this methodology all alkanethiol and 2-PET
glycine, cysteine, and glutamic acid) protected stable gold
protected Au25 cluster can be synthesized.
cluster came from Schaaff et al.227 in 1998. These authors
prepared polymeric Au(I)SG in solution which was later
reduced in a MeOH/H2O medium using NaBH4 as the isolated and assigned with approximate compositions. Later in
reducing agent. A mixture of solvents was used to control its 2005,229 nine such clusters were isolated through PAGE

Figure 5. (a) Optical spectra of all nine isolated clusters in Figure 4b. Reprinted from ref 229. Copyright 2005 American Chemical Society. (b)
Kohn−Sham (KS) orbital energy level diagram for the model cluster Au25(SH)18−. Each KS orbital is drawn to indicate the relative contributions
(line length with color labels) of the atomic orbitals of Au(6sp) in green, Au(5d) in blue, S(3p) in orange, and others in gray (those unspecified
atomic orbitals, each with a <1% contribution). The left column of the KS orbitals shows the orbital symmetry (g, u) and degeneracy (in
parentheses); the right column shows the HOMO and LUMO sets. (c) Theoretical absorption spectrum of Au25(SH)18−. Inset shows the
experimental absorption spectrum of Au25(PET)18 cluster. Peak assignments: peak 1 at1.8 eV, peak 2 at 2.75 eV, and peak 3 at 3.1 eV. Reprinted
from ref 41. Copyright 2008 American Chemical Society.

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separation (photograph provided in Figure 4b). After the [Aun(SG)m−xH]x− were observed in negative ion ESI MS.229
separation, individual bands were cut and in the above study The optical spectrum of Au25(SG)18 cluster (number 6 in
each one was extracted in water (photographs of the cluster Figure 5a) shows multiple features. The Aikens group has
solutions are given in Figure 4c). The corresponding clusters explained the origin of the optical spectrum through time-
were assigned to Au10(SG)10, Au 15(SG)13 , Au 18(SG)14, dependent density functional theory (TDDFT) calculations
Au22(SG)16, Au22(SG)17, Au25(SG)18, Au29(SG)20, Au33(SG)22, considering Au25(SH)18− as a model system.41 The correspond-
and Au39(SG)24 using ESI MS. Interestingly, the Au28(SG)16 ing Kohn−Sham molecular orbitals (MO) and atomic orbital
cluster reported by Schaaff et al.227 was comparable and was (AO) contributions are presented in Figure 5b. All the
reassigned here as Au25(SG)18. This first report of a precisely characteristic transitions are marked.
assigned and isolated Au25(SR)18 led to a revolution centered The calculated optical spectrum (Figure 5c) matches with
around this cluster. The main drawback of the above- the corresponding experimental one (inset of Figure 5c),
mentioned two synthetic routes is the low yield of the product especially in the spectral shape. The first excited state at 1.52 eV
formed. Zhu et al.,185 by using the Brust protocol with (peak 1) corresponds to a HOMO to LUMO transition (Figure
phenylethanethiol (PET), demonstrated that an increased yield 5b) which is essentially an intraband (sp to sp) transition. The
is achievable by a kinetically controlled synthesis for nature of the electronic energy levels is understood from the
Au25(SR)18. Since this report, several other methods have calculations. The peak at 2.63 eV (marked as “2” in Figure 5c)
been discovered to obtain good yield and highly pure arises from mixed intraband (sp to sp) and interband (d to sp)
Au25(SR)18 clusters (see Table S1 for more details). Yu et transitions (Figure 5b). The peak at 2.91 eV (marked as “3” in
al.192 synthesized the Au25(Cys)18 cluster in large scale through Figure 5c) arises principally from an interband transition (d to
a new CO-directed route, where CO has been used as the sp). Several other techniques also help in understanding the
reducing agent. Photographs of the reacting solutions at optical confinement of nanoclusters. The existence of gold-core
different times are shown in Figure 4d. Several other clusters and semi-ring gold state (see below) has been demonstrated
have also been synthesized using this methodology.262 They through ultrafast optical measurements.269−273 Miles et al.274
have also developed the NaOH-mediated NaBH4 reduction263 have reported temperature dependent electrochemical proper-
and protection−deprotection method264 for the synthesis of ties of quantum-sized clusters, from which they claim that the
thiolated Au25 nanoclusters. Limited examples of Au25(SR)18 HOMO−LUMO energy gap increases with decrease in
cluster synthesis have been discussed in this section, but it is temperature. Shibu et al.275 have shown the temperature
important to note that there are several reports on this topic dependency of photoluminescence of Au25(SR)18 cluster
alone. (discussed in detail in section 3.2.2). Although many research
groups have tried to investigate the origin of the optical
3.2. Evolution of the Electronic Structure properties of metal nanoclusters, some questions regarding the
The distinct electronic structures of atomically precise clusters electron−phonon interactions, coupling of gold core states with
merge into the continuous bands of metallic particles. the semi-ring states, nature of excitation states, etc., still remain
Absorption spectra resembling molecules have been seen in unanswered. Devadas et al.276 have tried to answer these
various well-defined clusters.265 In order to observe such questions from temperature dependent optical measurements
features, isolation studies of clusters have been performed from of Au25(SR)18 and Au38(SR)24 clusters. For most of the
the very early period of cluster science. An expanding array of nanocluster report, wavelength is converted to energy while
materials has confirmed the convergence of molecular bands to plotting. These nanoclusters show bands over a broad spectral
plasmonic features in a size dependent fashion, the threshold of window which appear like a hump. Thus, it is difficult to
which varies with the metal. While the changes have largely distinguish between two humps or peaks, which makes the
been seen in optical absorption, very few studies have observed above transformation useful. It simply uses277
a similar trend in photoluminescence. In many such studies, E = hc/λ (5)
optical peak shifts tending to the NIR are seen, yet the
disappearance of emission and shift into infrared are not However, it is not enough to make a proper plot in energy
observed. units. It must be noted that the signal values recorded by a
3.2.1. Optical Spectroscopy. A usual characteristic of spectrometer are really values per unit wavelength or per unit
monolayer protected ultrasmall metal clusters (with diameter energy. As wavelength and energy are inversely related, the
<2.2 nm) is an exhibition of prominent quantum confine- intervals in terms of wavelength are not evenly sized across the
ment.223,227,242,243,266,267 Therefore, optical spectroscopy is the energy spectrum. If the recorded signal is represented as a
best tool to identify nanoclusters. The appearance of step-like function f(λ), then the energy conversion yields
features (there may not be distinct steps all the time; rather f (E) dE = f (λ) dλ (6)
they may look like peaks) with spectral broadening in their
absorption profiles due to a molecule-like HOMO−LUMO Combining eqs 5 and 6, we get
transition and absence of the plasmon resonance confirms the
formation of such species. Conversion of the electronic band f (E) = f (λ)(dλ /dE) = f (λ)(d/dE)(hc /E)
structure to distinct energy levels leads to well-defined optical = −f (λ)(hc /E2) (7)
bands,242,243,268 which can be seen in the optical spectra shown
2
in Figure 5a of the PAGE separated bands shown in Figure 4b. The factor (hc/E ), known as the Jacobian factor, is used to
Clear absorption onsets appear in the 400−1000 nm range for scale the signal values along with wavelength conversion
these nine clusters, which are marked by downward arrows in [wavelength (in nm) = 1239.8/(energy (eV)]. Normally, it is
Figure 5a. The onsets are followed by humps (upward arrows plotted by multiplying the absorbance value with the factor 1/
in Figure 5a) that show a gradual blue shift with a decrease in W2, where W is the value in electronvolts corresponding to the
size. A series of peaks with composition corresponding to wavelength in nanometers.
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Coming back to the absorption spectrum of the Au25(SR)18 with the number of atoms in the cluster and this results in a
cluster,276 the peak maximum at 1.81 eV is shifted to 1.90 eV as larger gap between the adjacent energy levels for electrons and
temperature decreases from 323 to 78 K. A new vibronic holes. Photoluminescence of nanoclusters also depends on local
feature is also noticeable: the single peak at 1.81 eV (at 323 K), environments such as the protecting ligands and solvents.
which corresponds to the HOMO−LUMO transition for the Even though some of the gold clusters do not show visible
Au25(SR)18 cluster, resolves into two peaks with peak maxima at luminescence under UV light exposure, they can show emission
∼1.67 and ∼1.90 eV at lower temperatures. Three main points in the NIR region. Bigioni et al.253 in 2000 have shown the
could be confirmed from this study: (i) the absorption maxima emission of Au25(SR)18 clusters whose quantum yield (QY=
shifted to higher energies, (ii) the absorption feature became (4.4 ± 1.5) × 10−5) was found to be 5 orders of magnitude
sharper and new peaks emerged, and (iii) the oscillator strength more than that of bulk gold. This exceptionally large QY was
increased significantly with a decrease in temperature. attributed to intraband (sp to sp) transitions. Different possible
Experimental results fitted with models suggested that the excitations and emissions for Au25(SR)18 are depicted in Figure
nanocluster had significantly larger phonon energy due to the 7a.273 The cluster shows two distinct features (see Figure 7b): a
semi-ring gold, one of the structural units of the cluster (more strong emission (QY = ∼1 × 10−3) in the NIR region and a
details about the semi-ring have been explained in section weaker emission (QY = ∼10−6−10−7) in the visible region
3.2.2). which was further supported by steady state luminescence
An important difference among the three classes of noble experiments.249 The origin of fluorescence of Au25(SR)18
metal nanoparticles is their difference in optical absorption cluster can be explained from its structure. The Au25(SR)18
spectra. In fact, this is an immediate aspect of comparison, as cluster can be viewed as a core−shell structure where the core
the spectra are easily measurable in any laboratory. This is consists of 13 gold atoms (Figure 7a) and the shell is the semi-
illustrated with Figure 6, where the optical absorption spectra of ring made of Au2(SR)3 staples (detailed structure will be
explained under section 3.3). This semi-ring is responsible for
the fluorescence properties of Au25(SR)18 clusters. Wu and Jin
have shown the effect of different ligands on the fluorescence
properties of Au25(SR)18 clusters.281 According to their report,
the surface ligands can influence the fluorescence of clusters, in
two different ways: (i) ligands to the metal cluster core charge
transfer (i.e., LMCCCT) through the Au−S bonds, and (ii)
direct donation of delocalized electrons of electron-rich atoms
or groups of the ligands to the metal core. The high QY of
glutathione protected cluster compared to organic thiol
protected cluster is attributed to the presence of more
electron-rich atoms (O, N, etc.) or groups (−COOH,
−NH2) which facilitate the LMCCCT. A report of Wang et
al. also supports the role of ligands in the origin of fluorescence
of Au25(SR)18 clusters.282 Along with a solution phase study,
Shibu et al.275,283 have examined the solid state emission of the
Au25(SG)18 cluster in a range of temperatures of 80−300 K
Figure 6. UV/vis spectra of three different kinds of particles: (a) 25 (Figure 7c). The emission (a broad peak around 670 nm)
nm Au@citrate particles, (b) 3 nm Au@DDT MPC, and (c) intensity gradually increases with increase in temperature, and a
Au25(PET)18 clusters, respectively. Several differences are seen strong enhancement occurs after 160 K. No change in the peak
between clusters and nanoparticles (and MPCs). Extinction (label position confirms that the structure of Au25(SG)18 cluster is
on the right) is applicable for (a) and (b). intact. In contrast to the Au25(SR)18 cluster, Au38(SR)24 exhibits
a different behavior at very low temperatures. van Wijngaarden
three different particles are compared. The first one is the et al. have performed a solution phase temperature dependent
standard citrate protected gold nanoparticles in water. The study of Au38(SR)24 clusters.284 At 4 K, multiple bands exist as
other is MPC of 3 nm diameter, protected with DDT. The last fine structures, which overlap at higher temperatures and form a
is Au25(PET)18. While the first one has a sharp absorption broad peak. At higher temperature, the energy difference
attributed to plasmon resonance, the second one shows the between the emission bands is decreasing which increases the
same with significant broadening. The last one shows optical overlapping possibility to form a broad peak. Such broad
absorption features just like a dye molecule, but completely emission features are normally seen for metal quantum
different from a nanoparticle. This difference holds good for a clusters.31,150,187,285−302
majority of gold clusters, while for silver, some clusters also
3.3. Understanding the Composition, Structure, and
show one prominent feature, slightly distorted with shoulders,
Properties
but quite different from the plasmon excitation.
3.2.2. Photoluminescence. Photoluminescence, another A molecular system is understood entirely using several
distinct property of nanoclusters,278,279 arises because of the complementary tools. Mass spectrometry is one of the ways
transition between the HOMO and LUMO of the of understanding such a system, although this has been the
clusters.249,280 The luminescence from the bulk metals or single most important technique in this category of materials.
metallic particles is very inefficient because of the fast The ligand shell required molecular techniques to characterize
nonradiative relaxation due to their continuous band structure. the functional groups, intercluster interactions, solvation shells,
However, it is possible to increase the quantum yield by and changes in the media. These studies have revealed a wealth
decreasing the particle size, as the density of states decreases of information.
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Figure 7. (a) Schematic of the Au25 cluster and the energy diagrams which show the corresponding excitations and emissions. Reprinted from ref
273. Copyright 2010 American Chemical Society. (b) Excitation and emission spectra of Au25(SR)18 cluster protected with glutathione (red trace)
and hexanethiol (black trace), respectively. Reprinted from ref 249. Copyright 2002 American Chemical Society. (c) Temperature-dependent solid-
state emission of Au25(SG)18. Reprinted with permission from ref 275. Copyright 2009 World Scientific Publishing.

3.3.1. Advanced Mass Spectrometry. Researchers have protons, respectively. The right panel of Figure 8a shows the
shown the effectiveness of mass spectrometry to characterize deconvoluted mass spectra of Aun(SG)m derived from a series
clusters.29 It can give information about the core size as well as of multiply charged peaks. Among 1−9, fractions 2−7 are single
the ligand composition. Various advanced mass spectrometric clusters with precise size as can be seen from the mass spectral
techniques (e.g., MALDI TOF MS and HRESI MS) have been data. Compound 6 with corresponding mass of 10 437 Da has
used to understand the molecular formulas of purified clusters. been assigned as Au25(SG)18, which was previously assigned as
The earliest example of MALDI MS analysis of Au25(SR)18 Au28(SG)16 (10 415 Da).
cluster was by Schaaff et al.227 A molecular peak around 10.4 In general, ESI MS works well with aqueous soluble gold
kDa was assigned to an isolated glutathione protected gold clusters as they are easily ionizable, but for organic soluble
cluster, though an accurate composition was not established. clusters, this technique is not well-suited. In the recent past,
The exact composition was later found by Negishi et al.229 via several new methodologies have been implemented to
ESI MS measurements. They identified all nine isolated clusters overcome these problems. Researchers have shown that
based on their peak positions (Figure 8a) and isotopic ionization efficiency can be improved by adding external
distributions (Figure 8a, right panel). The clusters (1−9) ionizing agents such as cesium acetate (CsOAc).33 Ligand
were assigned as Au 10 (SG) 10 , Au 15 (SG) 13 , Au 18 (SG) 14, exchange with an ionizable ligand is another way to obtain good
Au22(SG)16, Au22(SG)17, Au25(SG)18, Au29(SG)20, Au33(SG)22, mass spectral features.303,304 Negishi et al.305 introduced an
and Au39(SG)24, respectively. The calculated spectrum of oxidation (by Ce(SO4)2) or a reduction (by NaBH4) process to
Au28(SG)16 has also been plotted for band 6 in Figure 8a to improve the ionizing capacity by enhancing the charge state of
illustrate that the assignment done by Schaaff et al.227 was the Au25(SR)18 cluster (see Figure 8b). The origin of magic
incorrect. This work by Negishi et al.229 was the first report of a stability of Au25(SR)18 cluster came out of the mass spectral
complete ESI MS assignment of a series of glutathione study. The spectra were measured for monopositive and
protected clusters. As depicted in Figure 8a, the negative-ion mononegative ions generated from neutral Au25(SR)18 cluster
ESI mass spectra of 1−9 have a series of peaks corresponding (Figure 8c). It can be noticed that ESI MS in the negative mode
to the formula, [Aun(SG)m−xH]x−, where n, m, and x represent shows a single peak corresponding to [Au25(SC6H13)18]− and,
the numbers of gold atoms, GS ligands, and dissociated interestingly, the positive mode also shows the
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Figure 8. (a) ESI mass spectra of isolated clusters, 1−9, prepared in a synthesis. Left and right panels are the parent and deconvoluted spectra of the
same, respectively. Red trace shows the corresponding calculated spectra for Aun(SG)m clusters with the corresponding n−m values. Reprinted from
ref 229. Copyright 2005 American Chemical Society. (b) Scheme of positively and negatively charged Au25(SR)18 cluster synthesis from neutral
Au25(SR)18 cluster. (c) Positive and negative mode ESI mass spectra of [Au25(SC6H13)18]−, [Au25(SC6H13)18]+, and [Au25(SC6H13)18] (1, 1′, and 2,
respectively). The notation (n, m−/+) represents [Aun(SC6H13)m]−/+. Reprinted from ref 305. Copyright 2007 American Chemical Society. (d)
Positive mode MALDI MS data of Au25(PET)18 cluster. Inset shows the expanded spectrum plotted with the calculated one (blue trace). Reprinted
from ref 306. Copyright 2008 American Chemical Society.

[Au25(SC6H13)18]− peak (marked by “+” sign to refer to the Mass spectrometry of clusters has advanced tremendously in
positive mode) with the counterion, TOA+. The positive mode the recent past. Precise mass assignment is possible for almost
mass spectrum of the [Au25(SC6H13)18]− cluster shows the any cluster system now. Excellent ways of ionization without
corresponding composition along with a possible dication, fragmentation, enhanced resolution at high masses, extremely
while the neutral species does not show any prominent feature high transmission, and high sensitivity have all contributed to
in either of the two modes as expected from its charged state. the advancements. Coupled with ion mobility analysis and MS/
Even after implementation of all the methodologies to improve MS, new properties of these clusters are being discovered
the ionizing efficiency, all clusters do not ionize by electrospray. today. To appreciate the power of new mass spectrometry, we
For such cases, MALDI MS is a good option but it requires a are presenting the ESI MS of Au 25 (PET) 18 (a) and
suitable matrix to get mass spectra at good resolution. Weak Ag25(DMBT)18 (b) in Figure 9. The spectra are remarkably
organic acids such as sinapinic acid, cinnamic acid, etc., were clean with no additional peaks except that of the molecular
ions. The molecular ions show well-defined isotopically
usually used as matrixes, but they were unable to prevent
resolved peaks, fully in agreement with the theoretical
fragmentation of clusters.
spectrum. The isotope structures are due to C, S, and H in
In 2008, Dass et al.306 illustrated the suitability of trans-2-[3-
the case of Au25(PET)18, while for Ag25(DMBT)18, all the
(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile elements contribute to the structure. Luo et al. were able to
(DCTB) as a matrix, particularly for Au25(PET)18 clusters trace all the stable intermediate species from reduction of
(Figure 8d). A comparison of the mass spectral quality of Au(I)thiolate to evolution of Au25(SR)18 clusters by high
Au25(PET)18 clusters using a range of matrixes showed that a resolution electrospray ionization mass spectrometry.311
much better resolution was achieved with this DCTB matrix. 3.3.2. MS/MS and Related Studies. Tandem mass
DCTB ionizes the molecule by electron transfer, whereas other spectrometry or MS/MS is the best analytical technique for
organic acids do the same with proton transfer, which is the understanding the fragmentation pattern of ions. Even though
main reason for its high effectiveness for Au clusters. Following this technique has been used for a variety of biological samples,
these reports, several groups have shown the extreme capability e.g. proteins of similar masses, it has not been explored much in
of MALDI MS using DCTB as the matrix.27,303,306−309 the context of atomically precise clusters. Fields-Zinna et al.312
8220 DOI: 10.1021/acs.chemrev.6b00769
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Chemical Reviews Review

structure in these systems.313 Ghosh et al.219 have shown a

detailed fragmentation pattern of Au18 clusters protected with
glutathione. Au18(SG)144− was seen in the ESI MS as a main
peak, which was selected for the MS/MS study (Figure 10b) for
further fragmentation. Two types of losses were seen, mainly
corresponding to m/z 32.5 and 4.5 (actually 32.5 × 4 = 130 and
4.5 × 4 = 18, respectively). The m/z 130 losses were due to
fragmentation from the peptide ligand. Cleavage of the
Cglutamic acid−Ncysteine bond generated two subsequent fragments
of masses m/z 130 (C3H8O3N) and m/z 176 (C5H8O3N2S).
The thiol containing fragment remained attached to the cluster
core, and the other fragment left was assigned as SGF.
Increase in collision energy leads to systematic fragmenta-
tion. Another type of loss corresponding to m/z 4.5 was due to
water (with 4− charge), which suggested the existence of
glutathione as an anhydride on the cluster surface. Water loss
was seen only after the initial fragmentation from Au18(SG)144−.
Thereafter, with increase in collision energy, water loss
occurred from a series of fragments. Interestingly, all the
major ions formed in the gas phase contained eight electrons
(including the ligand and the metal core) which are needed for
a closed shell configuration. This report points to a high
Figure 9. HR ESI mass spectra of Au 25(PET) 18 − (a) and
stability of these ions in the gas phase.
Ag25(DMBT)18− (b) clusters. Insets show the expanded views of the
molecular peaks plotted with the corresponding calculated patterns. It Ion mobility mass spectrometry (IMS) is an advanced
may be noted from inset of (b) that intensity oscillations are technique for understanding the structural details. In general,
reproduced exactly as predicted. Reprinted with permission from ref IMS separates ions based on their size, and more accurately
310. Copyright 2016 Nature Publishing Group. based on the collision cross section. Similar to liquid
chromatography, here, too, smaller ions that undergo more
performed the very first tandem mass spectrometric analysis of collisions elute faster than larger ions. For nanosystems, it has
Au25(SR)18 cluster. They conducted the low energy collision- been used mainly to understand several aspects of their
induced dissociation tandem mass spectrometry (CID MS/ fragmentation pattern and size distribution of gold nano-
MS) study of mixed ligand (phenylethanethiolate (−PET) and particles. IMS also helps in understanding the fragments
methoxy penta(ethylene glycol) thiolate (−SPEG)) protected generated from them such as Au4(SR)4 which are often seen in
Au25 clusters. The spectrum showed the generation of lower m/ the mass spectrum of Au25(SR)18. The same has also been
z fragment ions (Figure 10a) derived from found in the cases of Au38(PET)24 and Au68(PET)34 clusters.
[Na4Au25(PET)8(SPEG)10]3+ (m/z 2929). Several fragments But, no such species has been found as a staple from the crystal
of the type AuL2, Au2L3, etc., were observed along with the structure, which suggests that this fragment is generated under
Au4L4 fragment, which confirmed the occurrence of the semi- the mass spectral conditions. Fields-Zinna et al. have shown the
ring rearrangements on the surface of the cluster. Analogous formation of such a tetrameric ion in tandem mass
fragments have also been observed for bigger clusters such as spectrometric conditions from Au25(SR)18 clusters.312 Through
Au38(SR)24, Au144(SR)60, etc., indicative of a similar surface this technique, it is possible to reduce such fragmentation

Figure 10. (a)ESI-QQQ-MS/MS spectrum of PEGylated Au25 sample (in methanol with excess NaOAc) after fragmentation under CID conditions.
Brackets and arrows indicate AuNLM species, where L is the distribution of ligands (SC2Ph and SPEG) in which SPEG is more prominent. Reprinted
from ref 312. Copyright 2009 American Chemical Society. (b) MS/MS spectra of [Au18SG14]4− cluster with increasing collision energy (from
bottom to up). The label n represents the number of glutathione ligands fragmented, and p represents the number of water losses. Inset at the
bottom shows the characteristic cleavage of a bond in glutathione. Reprinted from ref 219. Copyright 2012 American Chemical Society.

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Figure 11. Crystal structures of Au18(SC6H11)14 (a), Au20(TBBT)16 (b), [Au23(SC6H11)16]− (c), Au24(SAdm)16 (d), Au25(PET)18 (e),
[N(C8H17)4][Au25(PET)18] (f), Au28(TBBT)20 (g), Au30S(S-t-Bu)18 (h), Au36(SPh-tBu)24 (i), Au38(PET)24 (j), Au40(o-MBT)24 (k), Au52(TBBT)32
(l), Au92(TBBT)44 (m), Au102(p-MBA)44 (n), Au130(p-MBT)50 (o), and Au133(SPh-tBu)52 (p) clusters, respectively. In some cases, the complete
ligand structure is not shown. In such cases (b, e, f, g, i, j, n, o), only Au and S atoms are shown. Reprinted from refs 15, 41, 204, 317, 318, 320, 321,
and 323−325. Copyright 2008, 2010, 2013, 2014, 2015, and 2016 American Chemical Society. Reprinted with permission from refs 43 and 316.
Copyright 2012 and 2015 John Wiley & Sons. Reprinted with permission from refs 45 and 322. Copyright 2007 and 2015 American Association for
the Advancement of Science.

which results in increase in intensity of the low intensity peak. protection (Figure 11) have been identified up to the end of
Angel et al.314 have shown ion mobility MS/MS studies of October 2016. There are a few other reports of gold clusters
Au25(PET)18 cluster. From this IM-MS/MS study, it is possible with phosphine326−328 or mixed ligands42,47 (phosphine and
to distinguish between the fragments of the outer protecting thiols) protection, but in this section we will only discuss the
layer, made from six [−SR−Au−SR−Au−SR−] “staples”, and complete thiol protected gold clusters. Unlike inorganic
the Au13 core. Several fragmentation patterns with predominant clusters,329 obtaining a single crystal structure of protected
loss of Au4(SR)4 species were seen along with the other smaller noble metal clusters is very difficult primarily because of
fragments such as Au(SR)2−, Au2(SR)3−, Au3(SR)4−, and stability and sensitivity issues. The crystallization methodology
Au4(SR)5−. and solvents also play important roles in forming diffractable
3.3.3. Single Crystal Studies. Even though there are a crystals. For most cases, the vapor diffusion method works well,
number of reports of atomically precise gold clusters based on but concentrated cluster solutions are required for this case and
mass spectrometry and other characterization techniques, only the clusters must be highly pure.
some are available with single crystal structure. Crystal The earliest report of a single crystal structure of a thiolate
structures of only 15 clusters, namely Au18(SR)14,315,316 protected cluster is of Au102(p-MBA)44 made by Jadzinsky et
Au20(SR)16,317 Au23(SR)16,318 Au24(SR)16,319 Au25(SR)18,15,41 al.45 in 2007. The chiral nature of the cluster was also revealed
Au28(SR)20,320 Au30S(SR)18,321 Au36(SR)24,43 Au38(SR)24,204 by the crystal structure. In 2008, the Murray15 and Jin41 groups
Au40(SR)24,322 Au52(SR)32,322 Au92(SR)44,323 Au102(SR)44,45 reported the crystal structure of Au25(PET)18 clusters which
Au130(SR)50,324 and Au133(SR)52325 with complete thiol consisted of an icosahedral core, encapsulated with six
8222 DOI: 10.1021/acs.chemrev.6b00769
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 Table 2. Crystal Structures of Thiolated Gold Clustersa
shell
core characteristics M−M bond characteristics
no. no.
Au(SR)2 Au2(SR)3 bond average bond unit cell
cluster composition composition geometry composition motifs motifs others type bond dist (Å) dist (Å) geometry ref
Chemical Reviews

Au18(SC6H11)14 Au9 bioctahedral Au9(SC6H11)14 3 1 four Au4(SR)5 3.09 ± 0.23 triclinic 315,
316
Au20(TBBT)16 Au7 bitetrahedral Au13(SR)16 2 Au8(SR)8 ring and 5 2.88, 2.982, 2.72, − orthorhombic 317
Au3(SR)4 trimeric 2.74, 3.03
staple
[Au23(SC6H11)16]TOA Au15 cuboctahedron-based bipyramidal Au8(SR)16 2 − two Au3(SR)4 and four 3 2.96 ± 0.28, ∼2.93, 2.96 orthorhombic 318
−SR ∼2.7
Au24(SAdm)16 Au15 distorted cubocatahedral core Au9(SR)16 1 1 Au3(SR)4 3 2.704−3.490, 2.92 ± − triclinic 319
0.19, 3.03 ± 0.22
Au25(PET)18N(C8H17)4 Au13 icosahedral Au12(SR)18 0 6 − 3 3.02−3.12, 3.14− 2.95 triclinic 41
3.27, 2.80−2.81
[N(C8H17)4] Au13 icosahedral Au12(SR)18 0 6 − 3 2.79 ± 0.01, 2.93 ± 2.96 triclinic 15
[Au25(PET)18] 0.06
Au28(TBBT)20 Au20 rod-like kernel consisting of two Au8(SR)20 0 4 eight −SR 3 2.92, 2.87, 3.40 2.98 triclinic 320
interpenetrating cuboctahedral
Au30S(S-t-Bu)18 Au20 bicuboctahedral Au10S(SR)18 4 Au3(SR)4, SR, and − − − triclinic 321
μ3 S
Au36(SPh-tBu)24 Au4@ face centered cubic Au8(SR)12 0 4 − 2 2.81, 2.85 2.91 base-centered 43
Au24(SR)12 monoclinic

8223
Au38(PET)24 Au23 face fused bicosahedral Au15(SR)12 3 6 − − − 3.0 triclinic 204
Au40(o-MBT)24 Au25 snowflake-like Au25 kernel with tetrahedral units Au15(SR)24 6 three Au3(SR)4 5 2.78, 2.76, 2.90, − triclinic 322
coiled up into a Kekulé-like superstructure 3.01, 3.16
Au52(TBBT)32 Au32 segregated into 10 tetrahedral units Au20(SR)32 4 8 4 2.79 2.99 3.10, 3.62 − triclinic 322
Au102(p-MBA)44 Au79 icosahedral Au23(SR)44 19 2 − − 2.80−3.10 2.90 − 45
Au130(p-MBT)50 Au13@ ino-decahedral, ino-decahedral, pentagonal Au25(SR)50 25 0 − − − − monoclinic 324
Au42@ barrel
Au50
Au133(SPh-tBu)52 Au13@ icosahedral, icosahedral, vacant Au26(SR)26 26 0 − − − − monoclinic 325
Au42@ rhombiicosidodecahedral
Au52
a
Au92(SR)44 has not been presented here as it has a self-assembled monolayer structure323 which cannot be presented in this format.
Review

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Au2(SR)3 staples. Later in 2010, the total structure of protected gold clusters. Parker et al.333 have shown electron
Au38(PET)24 was solved by Qian et al.204 It is composed of a self-exchange dynamics of nanoparticle-coupled
bi-icosahedral core with three Au(SR)2 staples and six Au2(SR)3 [Au25(PET)18]0/1− by NMR line broadening. From the crystal
staples. The same structure had been predicted earlier in 2008 structure analysis, it has been observed that Au25(SR)18 cluster
by Pei et al.330 through DFT calculations using the “divide and has Au@Au12@Au12 type structure,41 where the first shell (shell
protect” concept.231 To construct the structure, the thiolate 1) surrounds the central Au atom to form an Au13 kernel that is
protected nanoclusters were divided in groups of [Au]a+a′[Au- further encapsulated by another shell (shell 2) of Au12 atoms. In
(SR)2]b[Au2(SR)3]c, where a, a′, b, and c are integers. In this this cluster, two types of thiolate binding modes were
formulation, [Au]a+a′ represents the gold core which satisfies identified: (I) 12-SR ligands which join the Au shells 1 and
the condition that the number of core “surface” Au atoms (a′) 2; (II) 6-SR ligands located on the Au12 shell 2. To determine
equals the sum of end points of the staple motifs (2b + 2c); b which of these thiolate binding modes is more stable, Jin’s
and c are numbers of different types of staple motifs. That is, group334 performed an NMR study focusing on the oxidation
each of the core surface Au atoms is protected by one end point resistance and thermal stability of the Au−S bond. In this
of the staple motif. This strategy was implemented based on the experiment, Au25(SG)18 was systematically oxidized using
reported crystal structures of [Au25(SR)18]− and Au102(SR)44, Ce(SO4)2 and a time dependent NMR was measured.
which can be represented as [Au]1+12[Au2(SR)3]6 and Assignments of all the peaks have been mentioned in another
[Au]39+40[Au(SR)2]19[Au2(SR)3]2, respectively. Therefore, for report.335 Protons attached with C7 atom of the ligand split
Au38(SR)24, the parameters a, a′, b, and c must satisfy the into two parts (because of chirality335) to form a doublet at 3.6
following conditions: (a + a′ + b + 2c) = 38, (2b + 3c) = 24, and 3.8 ppm corresponding to α-H of thiolate binding mode I
and a′ = (2b + 2c). Based on these, the possible combinations and another doublet at 3.3 and 3.4 ppm corresponding to α-H
are (i) [Au]2+24[Au(SR)2]12, (ii) [Au]3+22[Au- of thiolate binding mode II. The ratio of mode I to mode II is
(SR)2]9[Au2(SR)3]2, (iii) [Au]4+20[Au(SR)2]6[Au2(SR)3]4, 2:1. Upon addition of Ce(SO4)2, the doublet at 3.3/3.4 ppm
(iv) [Au]5+18[Au(SR)2]3[Au2(SR)3]6, and (v) was broadened and was almost lost after 6 h, which suggests
[Au]6+16[Au2(SR)3]8. Band gap analysis and a comparison of that binding mode II is comparatively weak and is attacked first
the calculated UV/vis spectra with experimental data predicted by the oxidant. In contrast, the doublet at 3.6/3.8 ppm
combination iv as the preferred structure for Au38(SR)24. The remained unaffected even after 5 days, from which it can be
Au38(SR)24 cluster is also chiral because of the specific concluded that binding mode I is much stronger than binding
arrangement of the staples, which will be discussed later in mode II. Thus, with an NMR study, one can correlate the
greater detail. structural stability in terms of Au−S bond strength under an
In general, the single crystal data suggests that most of the oxidative atmosphere. The effect of charge state on NMR of
nanoclusters have a core−shell structure (Figure 11). The core Au25(SR)18 cluster has been demonstrated by Venzo et al.182
is composed of 15, 13, 20, 28, 23, and 79 atoms for Au23, Au25, Although this review is focused on thiolated clusters, it is
Au28, Au36, Au38, and Au102, respectively (the structural important to mention that 31P NMR is also very useful in
information about the new clusters such as Au18, Au20, Au24, structural analysis of phosphinated gold clusters.336,337 Clayden
Au30, Au40, Au52, Au130, and Au133 are described in Table 2). In et al.338 have shown the importance of high resolution solid and
each case, the core is surrounded by a shell, which is composed solution state 31P NMR to understand the dynamics of
of two types of staple motifs: Au(SR)2 and Au2(SR)3. In smaller phosphinated gold clusters. There are several such reports
clusters such as Au25(SR)18, the latter one is predominant, but where 31P NMR and 1H NMR have been used as character-
in larger clusters, e.g. Au102(SR)44, the Au(SR)2 motif ization tools, and many of them are tabulated in Table S1.
dominates. In a few cases (e.g., Au23 and Au28 clusters) 3.3.5. Other Spectroscopies. Among other spectroscopic
bridging −SR motifs are also present in their structure. techniques, infrared spectroscopy has mostly been used to
Typically, the Au−Au bond distance average varies between understand the binding mode of the thiol group in metal
2.95 and 3.0 Å in these clusters. These structural illustrations nanoclusters and nanoparticles. The most common feature is
help us understand atomically precise gold clusters in a much the disappearance of S−H vibrational band to confirm that the
deeper way. More details are provided in Table 2. Recently, binding of ligand occurs through the sulfur atom. In general,
Azubel et al.331 have determined the structure of Au68NP at other features of IR spectra of the clusters tend to be identical
atomic resolution by a new approach employing aberration- with those of the corresponding free ligands. Farrag et al.339
corrected transmission electron microscopy with minimal demonstrated that Au25(PET)18 showed a distinct shift of the
electron dose and with electron density mapping. Li et al. aromatic C−H stretching band (appearing at 3000−3100
have shown such a possibility for Au25 and Au39 clusters to cm−1) compared to the free PET ligand. This unusual shift of
understand their size and shape.332 The structure obtained for the C−H stretching band from 3030 to 3100 cm−1 to below
the 68 atom cluster was correlated with DFT calculations. The 3000 cm−1 was attributed to an electronic interaction of the
68 gold atoms are described as a 13-atom cuboctahedron (with aromatic rings of the ligands with each other or with the gold
an atom in the center) surrounded by 24 atoms extending the core. But other PET protected Au38 and Au144 clusters showed
fcc-like framework and by an additional 31 atoms deviating the same features as seen for the PET ligand (except the S−H
from fcc packing. Unlike the case of Au102, this cluster was band). This was possibly due to an increase in the cluster size,
found to be less symmetric. This technique opens up another which prohibited the close proximity of the ligands.
way to look at the structures of clusters as structure Dolamic et al.340 carried out far-infrared spectroscopic
determination through SXRD has not been an easy task so studies of a few well-defined thiolate (2-phenylethanethiolate)
far. More detail structural analysis of various gold clusters can protected gold clusters, such as Au25, Au38, Au40, and Au144. The
be found in the recent review article by Jin et al.6 spectra showed characteristic features for every individual
3.3.4. NMR Spectroscopy. NMR spectroscopy has been cluster, but the differences were very small. Quantification of
used to investigate the structural stability of monolayer monomeric and dimeric staple units was not possible as there
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was no systematic variation, but the conformation of phenyl- the Au−Au bonds have different stiffnesses depending on their
ethanthiolate could be predicted. The band at 490 cm−1 is lengths.
associated with an out-of-plane vibrational mode of the phenyl 3.4. Other Gold Clusters
moiety coupled to a C−C−S bending mode, which is an
There are several reports of other gold clusters besides the well-
indication of the anti conformation of phenylethanethiolate. defined clusters mentioned above, and in most of the cases, the
Crystal structures of Au25(PET)18 and Au38(PET)24 show the composition was identified using mass spectrometry. It is
presence of 14:4 and 14:10 anti:gauche conformations, important to mention here that as Au25(SR)18 cluster has been
respectively. Mostly, anti conformation of the S−C−C phenyl explored in much greater detail than any other one, it has been
unit has been observed for all the cases. Few units with gauche considered here as a representative of atomically precise
conformation were also noticed which lead to a shift of this clusters. Several clusters have been tabulated in Table S1 with a
band toward lower wavenumbers. Bands at 210−280 cm−1 brief description. Along with thiol protection, protein protected
region have been assigned to Au−S vibrations. Parker et al.333 nanoclusters52,55,370−400 such as Au@BSA,213 Au@lysozyme,401
have found the Au−S vibrational band near 290 cm−1 for the etc., are also known and most of them are highly luminescent in
Au25(PET)18− cluster from Raman spectroscopy. The band nature. For these systems, the number of metal atoms has been
shows a lower energy shift by 24 cm−1 for the neutral Au25 found from MALDI MS data after subtracting the protein mass
cluster. Varnholt et al.341 have investigated the influence of (more details about protein protected cluster can found in
thiolate ligands on the Au−S vibrations and the effect of cluster section 7). There are a few clusters which do not have well-
size for a series of clusters such as [Au25(PET)18]0/−, defined mass spectra, but they have step-like optical
Au25(CamS)18 (CamS = 1R,4S-camphorthiol), Au38(PET)24, features.402−405 Selenolate,406−408 tellurolate,409 DMF,410 phos-
Au40(PET)24, and Au144(PET)60. phine,157,160,161,163,164,176,411−413 polymer,414−417 alkyne,418−421
Considering the molecule-like nature of these atomically mixed-ligand,42,47 etc., protected clusters have also been
precise gold clusters, their electrochemical properties are reported by various research groups.
interesting topics to explore, and voltammetry is a powerful
technique to investigate the HOMO−LUMO gap or electron 4. ATOMICALLY PRECISE SILVER CLUSTERS
transfer in such systems.1,342,343 The difference between the Even though gold and silver belong to the same group of the
first oxidation and reduction potentials of a cluster is periodic table, they show distinctly different properties in many
considered as the HOMO−LUMO gap.1 Band gaps of several cases. Compared to gold, silver in zerovalent state is much
gold clusters such as Au25(SR)18 (∼1.65 V), Au38(SR)24 (1.2 more reactive and easily oxidizable, making it difficult to
V), and Au75(SR)40 (0.74 V) have been measured electro- explore its clusters in greater detail.48 The Dickson group has
chemically.250,252,344,345 The Murray group has studied these studied extensively fluorescent silver clusters made under
extensively starting from 2004.1,250,252,344 From the square wave dendritic and DNA templates.422−447 The Pradeep group has
voltammetry analysis (SWV) of Au25(SR)18, four peaks at tried to examine the chemistry of silver clusters using mass
−2.09 V (R1), − 0.44 V (O1), − 0.08 V (O2), and 0.66 V spectrometry and other characterization tools.11,14,16,37 Other
(O3) [vs Ag/Ag+] have been found which are due to groups such as those of Bigioni, Kitaev, Bakr, etc., are also
Au 2 5 (SR) 1 8 − / 2 − , Au 2 5 (SR) 1 8 0 / − , Au 2 5 (SR) 1 8 + / 0 , and working on silver clusters.13,28,30,448,449 Crystal structures of a
Au25(SR)182+/+ couples, respectively. R1, O1, O2, and O3 few mixed ligand protected silver clusters have been solved,39,40
correspond to reversible reduction peak 1 and reversible but well-defined mass spectra were missing for a few years.
oxidation peaks 1, 2, and 3, respectively. The Lee group has Crystal structures of the highly stable Ag44(SR)30 cluster
shown the electrochemical properties of Au25 clusters in which (initially known as intensely and that of broadly absorbing
the water-soluble 3-mercaptopropylsulfonate protected Au25 nanoparticles (IBAN)) 450 with diverse ligands and
clusters were phase transferred to different organic media and Ag25(SR)1846 cluster have been determined, which has
the solvent dependency was studied electrochemically.346 enhanced our understanding of Ag cluster systems.44 It is to
Depending on solvent polarity, the HOMO−LUMO energy be noted that Ag44(SR)30 was initially synthesized by Bakr et
gap varies from 1.39 to 1.66 V. In another report, they made al.450 and Ag25(SR)18 was reported earlier by Cathcart et al.451
different mixed ligand protected (phosphine and thiols) and Chakraborty et al.216
bicosahedral Au25 clusters and found that the electrochemical 4.1. Early Synthesis of Silver Clusters
and optical properties are drastically different from the Even though there were several attempts to make atomically
complete thiol protected Au25 clusters.347 Utilizing these precise silver clusters with the protection of different
electrochemical properties, this cluster has been made in ligands,179,450−454 in those early days none of them had
ionic liquid form which shows effectiveness in glucose detailed mass spectral data. Mrudula et al. measured the
sensing.348 molecular mass of a 7 kDa cluster using MALDI MS, but it was
Several other spectroscopic techniques such as magnetic not enough to identify the system precisely.191 Wu et al.455
circular dichroism (MCD),349−351 electron paramagnetic have shown the very first ESI MS analysis of a monolayer
resonance (EPR),352−354 extended X-ray absorption fine protected silver cluster, whose precise composition was
structure (EXAFS),355−363 Mössbauer,364−366 X-ray diffraction determined to be Ag7(DMSA)4. It was synthesized using
(XRD),367 magnetophotoluminescence spectroscopy,368 etc., AgNO3 in a suitable solvent where ligand with an effective ratio
have also been used for detailed understanding of the structure (normally 1:N with respect to silver, where N = 2, 3, 4, 5, ...,
of atomically precise gold clusters, and a comprehensive list can 10) was added and the mixture was cooled in an ice bath
be found in Table S1. A recent example of the power of EXAFS (Figure 12). Then the required amount of NaBH4 in an ice-
was shown by Yamazoe et al.,369 where hierarchy in the bond cold solvent was added to reduce the metal, and the solution
stiffness in clusters such as Au25(PET)18, Au38(PET)24, and was stirred continuously for a few hours. Cluster formation was
Au144(PET)60 has been measured successfully. They found that observed clearly by a color change, monitored with UV/vis
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clusters under boiling water condition.456 Chakraborty et al.

have reported the synthesis of silver clusters using sunlight in a
gel cavity.21 Here, the gel cavity controls the size of the cluster
formed by sunlight mediated reduction. Bakr et al.450
synthesized intensely and broadly absorbing nanoparticles
(IBANs), mentioned previously, which showed molecule-like
optical absorption features. The cluster was formed using a
solution phase route, in which a silver salt solution was reduced
in the presence of the capping ligand, 4-fluorothiophenol
Figure 12. Photographs of Ag7(DMSA)4 cluster synthesis. From left to
right: (a) ethanol solution of AgNO3, (b) 4 h after the addition of (4FTP). Briefly, 4FTP was stirred with a silver precursor
DMSA, and (c) 12 h after addition of NaBH4. Reprinted from ref 455. (4FTP:Ag = 2:1) in N,N-dimethylformamide (DMF) for 15
Copyright 2009 American Chemical Society. min. Then a solution of NaBH4 in DMF (NaBH4/Ag = 4:1)
was added to the reaction mixture. The color of the solution
spectroscopy. The cluster was purified by precipitation, and the changed to brown and darkened further with time. Initially,
precipitate was further extracted by a suitable solvent to get the plasmonic nanoparticles were formed which showed an
purified cluster. Following this report several new method- absorption band at 450 nm. Stirring was continued for 4 h,
ologies have been developed to synthesize atomically precise then a small volume of water was added, and the reaction
silver clusters. Some of them will be discussed in section 4.2. mixture was left in the freezer (−4 °C) for several days. Under
4.2. New Routes for Silver Clusters these conditions, the plasmonic feature changed to a new
molecular peak with five intense and four broad bands.
Similar to gold clusters, various synthetic methodologies have Ag 29 (BDT) 12 457 and the “golden silver” nanoparticle,
been implemented for the synthesis of monolayer protected Ag25(DMBT)18,46 have been synthesized through a one-step
silver clusters and most of them have been discussed in the solution phase route using methanol−DCM solvent mixture.
perspective article.48 Recently, the Pradeep group developed Several other methodologies are now available for synthesizing
two new routes for synthesizing atomically precise clusters. The
atomically precise silver clusters, and a brief description of each
first one is a solid state route,37 where a solid silver precursor
one is given in Table 1.
was taken in an agate mortar and ground well, then the
corresponding thiol was added, and the mixture was ground for Box 3. Synthesis of Ag44(FTP)30 Cluster through the “Solid
a few minutes (Figure 13). This results in a change in color that State” Route

About 20 mg of AgNO3 and 12 mg of PPh4Br were ground

thoroughly in an agate mortar and pestle for 5 min. About 76
μL of 4-fluorothiophenol was added to it in one shot, and the
mixture was ground for about 3 min more. Dry NaBH4 (45
mg) was added and the mixture was ground until the pasty
Figure 13. Photographs representing the changes during cluster mass became brown in color. This was extracted with 7 mL of
synthesis (a−c) through a solid state route. (a) Silver nitrate taken in a dichloromethane and kept undisturbed at room temperature
mortar; (b) solid thiol was added and ground well followed by the until UV/vis spectra showed all the characteristic features of
addition of solid NaBH4; (c) The mixture was stirred well and Ag44(SR)30 cluster. Then it was purified by repeated
extracted in ethanol. Reprinted from ref 37. Copyright 2010 American precipitation using methanol. Finally, the cluster was extracted
Chemical Society. in DCM. Using this technique, 4-FTP, 3-FTP, and 2-FTP
protected clusters can be synthesized.
confirms the formation of thiolate. Then solid NaBH4 was
Purification is the key step for synthesizing atomically precise
added and grinding was continued for a few minutes, which was
silver clusters. A convenient way to purify the material is to
followed by the addition of ethanol. Ethanol serves two
precipitate them using methanol (in aqueous or organic
important roles here: first, it helps to reduce the metal by
media). Similar is the case for the solid state route where
providing a limited supply of water which controls the size of
washing with solvents such as ethanol/methanol serves the
the cluster and, second, it washes out the excess ligands, as
purpose of cleaning.37 Kumar et al.13 have shown the separation
normally clusters are insoluble in ethanol. The mixture was
of glutathione protected silver clusters using PAGE, and 16
then centrifuged well for a few minutes and the precipitate
discrete bands were isolated with distinct UV/vis features. In a
containing atomically precise clusters was extracted in
recent report on Ag44(MBA)30 cluster synthesis, protonation is
appropriate solvents. Several clusters such as Ag9,37 Ag32,35
identified to be important for purification, as MBA in thiolate
Ag44,36 and Ag15216 have been synthesized using this procedure.
form is not soluble in DMF.44 Therefore, in order to extract the
The second synthetic procedure follows a high temperature
cluster in DMF in pure form, protonation is necessary. In
route.11 The corresponding silver precursor and ligand mixture
another report on the Ag44(4-FTP)30 cluster, a two-phase
were stirred for a few minutes at 70 °C, and then the required
(methanol−DCM) method has been used first to synthesize
amount of formic acid was added. Here, formic acid was used
the cluster and, after the synthesis, the cluster then goes into
instead of the traditional reducing agent, NaBH4. The
the organic (DCM) layer.222 Careful removal of the aqueous
temperature was kept constant throughout the reaction. The
layer and subsequent washing generated the purified cluster.
color changes from light yellow to reddish brown in 3 h, which
confirms the formation of the cluster. The slow reducing 4.3. Well-Defined Mass Spectral Characterization
capacity of formic acid and high temperature control the cluster As discussed in section 3.3, mass spectrometry is an ideal tool
size. Similarly, Zheng et al. synthesized luminescent silver to identify the precise composition of quantum clusters. As
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Figure 14. (a) MALDI MS spectra of Ag152(PET)60 cluster taken at threshold laser power. DCTB was used as the matrix. Reprinted from ref 16.
Copyright 2012 American Chemical Society. (b) The HRESI MS of Ag44(SR)30 cluster (black trace) protected with p-fluorothiophenol. Blue trace is
the calculated spectrum of the corresponding cluster. Reprinted with permission from ref 30. Copyright 2012 Royal Society of Chemistry. (c) and
(d) represent the ESI mass spectral data of Ag29(BDT)12 and Ag25(DMBT)18 clusters. Insets in both show the expanded views of the molecular
peaks along with the calculated patterns. Reprinted from refs 457 and ref 46. Copyright 2015 American Chemical Society.

silver has two isotopes, namely, 107 and 109 in a 50:50 ratio, IBANs450 were identified by Harkness et al.30 in 2012. Based
we expect the MS peaks of silver clusters to be more complex on isotopic distribution, the cluster was assigned as Ag44(4-
and broader than the corresponding gold clusters (having one FTP)304−. The experimental MS spectrum (Figure 14b)
isotope 197Au). Ag nanoclusters are highly fragile under the matched exactly with that obtained from calculations, and its
mass spectral conditions, so getting well-resolved mass spectra peak resolution was ∼0.25 mass unit. The extreme stability of
is a challenging task and most of the time only fragments are this cluster is due to its closed shell configuration ((44 − 30) +
observed. As mentioned earlier, Ag7(DMSA)4 cluster is the 4 = 18 electrons). The corresponding selenolate analogue of
earliest example of a Ag nanocluster whose composition was Ag44 cluster also showed clear isotope distribution in its ESI
determined precisely via MS.455 Several silver clusters have mass spectrum, for the 2−, 3−, and 4− ions.36 Recently
been identified by the Pradeep group using mass spectrome- discovered Ag29(BDT)12 and Ag25(DMBT)18 clusters show
try.11,14,16,37 MALDI MS can also be a good tool when used clean and high resolution mass spectra as presented in Figure
with a suitable matrix to identify the molecular peak, but the 14, parts c and d, respectively.
peak for Ag nanoclusters appears much broader than that for Along with ESI MS, Wu et al.455 performed MS/MS analysis
the corresponding gold clusters. As a result, it is difficult to of Ag7(DMSA)4, wherein they selected the dianion, [Ag7L4 −
predict the precise composition using MALDI MS. For this 3H + 2Na]2− (m/z 759.57) as the parent ion whose
reason, the silver clusters reported by Mrudula et al.191 showed fragmentation was analyzed with increase in collision energy.
a broad peak centered at m/z 7 kDa, but could not be assigned At low voltage (10 V), the parent ion loses a neutral fragment
to a specific composition. The Ag152(SR)60 cluster16 was found through C−S bond cleavage. At high voltage (25−40 V), the
to have a sharp molecular peak at m/z 24 610 (Figure 14a) and rest of the ligands disintegrate, but one S atom from each ligand
a full width at half-maximum (fwhm) of 1.3 kDa in its MALDI continues to be linked to the cluster core to form Ag7S4−. At a
MS spectrum. A dication at m/z 12 300 was also seen which still higher voltage, smaller fragments such as Ag6S4− and Ag5S4
further supported the composition. Varying the laser intensity were observed. The presence of four valence electrons was
led to systematic fragmentation of the cluster. Enhanced confirmed from this study, which explains the stability of such a
stability of the system can be attributed to the presence of the cluster.
magic number of electrons (152 − 60 = 92) that results in a In order to fragment ions of such high masses and multiple
closed shell electronic structure. Rao et al.37 reported the mass chemical bonds, collision induced dissociation is inadequate.
spectral identification of Ag9(H2MSA)7 cluster synthesized The energy imparted in collision with gas phase partners is not
through a solid state route. Guo et al.28 have shown a series of enough to cause fragmentation. In this context, surface induced
multiply charged peaks for the [Ag32(SG)19]q− cluster with a dissociation has been found to be a useful method. Here,
well-defined isotopic distribution. The compositions of collision of the ions with a solid surface is used to impart the
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Figure 15. Optical micrographs of typical crystals of M4Ag44(p-MBA)30 ((a) episcopic and (b) diascopic illumination), Ag44(4-FTP)30(PPh4)4 (c),
Ag29(BDT)16TPP4 (d), Ag25(DMBT)18−(PPh4)+ (e) and [Ag67(SPhMe2)32(PPh3)8]3+ (f) clusters, respectively. Reprinted with permission from refs
44 and 222. Copyright 2013 Nature Publishing Group (for (a), (b), and (c)). Reprinted from refs 457 and 46. Copyright 2015 American Chemical
Society (for (c) and (d)). Reprinted from ref 459. Copyright 2016 American Chemical Society (for (f)).

required activation energy. An early example of this has been Box 4. Crystallization of Ag44(MBA)30 Cluster
demonstrated recently for the Ag11(SG)7Nan3− cluster.458
Unprecedented charge stripping of the ion from −3 to −2 to First, the cluster has to be purified by repeated protonation
even −1 was seen at 40 V laboratory collision energy. Several and precipitation steps using citric acid and toluene,
fragments due to AgSG, Ag, and SG losses were seen with respectively. Then the cluster is extracted in HPLC grade
increasing collision energy. distilled DMF (without even traces of water). Note that the
4.4. Single Crystal Studies cluster concentration should be high (>50 mg/mL). This
Because of the reduced stability, aerial oxidation, and less purity purified cluster is then kept under an argon atmosphere
of silver clusters, formation of diffractable crystals is difficult for (should have an outlet) for solvent evaporation at low
silver clusters. A few reports are known for mixed ligand temperature (around 20 °C). After 2−3 days, crystals appear
(phosphine and thiol) and complete thiol protected silver as dark brown diamond shaped objects, which can be seen by
clusters. Optical microscopic images of crystals of a few optical microscopy.
reported silver clusters are presented in Figure 15. More details
about the unit cells and structural details are presented in Table 16d).457 Interestingly, the cluster has an icosahedral core similar
3. Yang et al.39 reported the single crystal structure of a mixed to Au25(SR)18, which is protected with a shell consisting of
ligand protected Ag14 cluster (Figure 16a) in 2012. In the Ag16S24P4. There are two types of silver atoms in the shell.
subsequent year, the authors also resolved the structures of Ag16 Twelve silver atoms connected with the 12 surface silver atoms
and Ag32 clusters (Figures 16b,e) protected by mixed ligands.40 (as four Ag3S6 crowns) of the core giving rise to four
As can be seen from Figure 16a, the Ag14(SC6H3F2)12(PPh3)8 tetrahedrally oriented trigonal prisms. The remaining four silver
cluster contains an octahedral Ag64+ core which is encapsulated atoms face capped the core at four tetrahedral positions (as four
by eight cubically arranged [Ag+(SC6H3F2−)2PPh3] in a Ag1S3P1). The “golden silver” Ag25(DMBT)18 cluster has a
tetrahedral fashion that shares one corner (i.e., SC6H3F2−) structure similar to that of Au25(SR)18, i.e. an icosahedral core
between them. Another important characteristic of this cluster containing a central Ag which is then surrounded by six
is that all the thiolate ligands bind to three Ag atoms and no Ag2(SR)3 motifs (Figure 16c). Very recently, Alhilaly et al. have
staple motifs are found unlike in the case of gold clusters (i.e., discovered an unusual box-shaped crystal structure of
Au(SR)2 or Au2(SR)3). Crystal structures of Ag44 clusters [Ag67(SPhMe2)32(PPh3)8]3+ cluster.459 The nonspherical
protected with p-mercaptobenzoic acid and p-fluorothiophenol shape is because of its electronic instability as it is a 32
have also been solved (Figures 16f,g). Single crystal structures electron system which does not have a closed shell electronic
suggest the existence of a hollow cage core and completely structure. Yang et al. in their recent report solved crystal
different type of staples surrounding the core (different from structures of plasmonic twinned silver nanoparticles with
other staples reported so far for both Au and Ag clusters). m o l ec u l a r f o r m u l a s [ A g 1 3 6 ( S R ) 6 4 C l 3 Ag 0 . 4 5 ] − a n d
The hollow cage containing 12 silver atoms arranged in an [Ag374(SR)113Br2Cl2], respectively.460 These are the largest
icosahedral fashion is surrounded by 20 silver atoms to form a thiolated metal nanoparticles solved so far by single crystal
keplerate structure with a total of 32 silver atoms. The Ag12@ studies.460 Ag136 and Ag374 clusters can be described as 5-fold
Ag20 core is further encapsulated with six Ag2(SR)5 staples twinned cores enclosed within related structurally distinctive
octahedrally. The average Ag−Ag bond distance in the core is Ag−SR complex shells. The former one consists of a
much shorter than in the bulk, suggestive of strong Ag−Ag pentagonal bipyramidal core of 54 Ag atoms, whereas the
metal bonding in the cluster. The crystal structure of a dithiol latter one has an elongated pentagonal bipyramidal core (ino-
protected silver cluster, Ag29(BDT)12(TPP)4 [BDT, benzene- decahedron) with 207 Ag atoms.460 Such 5-fold twinned metal
dithiol; TPP, triphenylphosphine] has been solved (Figure cores have been seen for a few gold clusters such as Au10245 and
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 Table 3. Crystal Structures of Some Silver Clusters
shell
core characteristics M−M bond characteristics
no. M(SR)2 average
and M2(SR)3 bond dist unit cell geom-
cluster composition composition geometry composition motifs others bond dist (Å) (Å) etry ref
Chemical Reviews

Ag14(SC6H3F2)12(PPh3)8 Ag64+ octahedral [Ag8(SR)12(PPh3)8]4− − [Ag+(SR)2PPh3] 2.81−2.85 2.83 primitive 39

Ag16(DPPE)4(SC6H3F2)14 Ag86+ nearly rhombus Ag4 unit capped by [Ag8(DPPE)4(SC6H3F2)14]6− − [Ag+(SR)2DPPE] 2.694−3.040 2.845 − 40
two Ag2 units above and below
the rhombus
Ag25(DMBT)18PPH4 Ag13 icosahedral Ag12(DMBT)18 6 Ag2(DMBT)3 − 2.7486−2.7847, 2.8209−2.9975 − triclinic 46
Ag29(BDT)12(TPP)4 Ag13 icosahedral Ag16S24P4 − Ag3S6, Ag1S3P1 2.77−2.92 2.77 and cubic 457
2.92
[Ag32(DPPE)5(SC6H3F2)24]2− Ag2212+ pentagon face-sharing bi(pentago- [Ag10(DPPE)5(SC6H3F2)24]14− − [Ag+(SR)2DPPE] 2.657−3.089 2.917 − 40
nal antiprism) Ag17 unit that is
side-capped by one Ag atom and
one near-square Ag4 unit at the
opposite direction
Ag44(SR)304− Ag12@Ag20 icosahedral, hollow cage Ag12(SR)30 − Ag2(SR)5 2.829, 2.846, 3.190 2.83 triclinic 44,
222
[Ag67(SPhMe2)32(PPh3)8]3+ Ag23 Ag13 cuboctahedron sharing with [Ag44(SPhMe2)32(PPh3)8] 4 Ag(SR)2 8 Ag(SR)3PPh3 2.846−3.048, 2.860, 2.806, 2.910 2.9195, orthorhombic 459
Ag8 crowns to form Ag21 metal connected to 2.860
core, which is again connected 2 Ag16 bowls
with two Ag atoms
Ag136(SR)64Cl3Ag0.45− Ag54 pentagonal bipyramid of 54 Ag Ag82(SR)64Ag0.45 − − − 2.870 triclinic 460
atoms

8229
Ag374(SR)113Br2Cl2 Ag207 elongated pentagonal bipyramid Ag207(SR)113 − − − 2.882 rhombohedral 460
(ino- decahedron)
Review

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Figure 16. Crystal structures of Ag14(SC6H3F2)12(PPh3)8 (a), Ag16(DPPE)4(SC6H3F2)14 (b), Ag25(DMBT)18−(PPh4)+ (c), [Ag29(BDT)16]TPP4 (d),
[Ag32(DPPE)5(SC6H3F2)24]2− (e), Na4Ag44(MBA)30 (f), Ag44(4-FTP)30(PPh4)4 (g), [Ag67(SPhMe2)32(PPh3)8]3+(h), Ag136(SR)64Cl3Ag0.45− (i), and
Ag374(SR)113Br2Cl2 (j), respectively. In (a), only the Ag core and S atoms are shown. For (i) and (j), left and right sides represent the top and side
views, respectively. Reprinted with permission from refs 39 and 40. Copyright 2012 and 2013 Royal Society of Chemistry (for (a), (b), and (e)).
Reprinted with permission from refs 44 and 222. Copyright 2013 Nature Publishing Group (for (f) and (g)). Reprinted from refs 457 and 46.
Copyright 2015 American Chemical Society (for (c) and (d)). Reprinted from ref 459. Copyright 2016 American Chemical Society (for (h)).
Reprinted with permission from ref 460. Copyright 2016 Nature Publishing Group (for (f) and (g)).

Figure 17. (a) MALDI MS spectra (collected in positive mode) of silver clusters prepared in solution. The spectra show a series of clusters with peak
maxima ranging from 10.2k to 70.9k. Almost all of them (except [vi] and [vii], which have some other features with reduced intensity) show sharp
single features which confirm the formation of one dominant cluster in each case. The fwhm varied from 1.5 to 5 kDa. The peaks (from bottom to
top) were assigned as Ag55(PET)31 [i], ∼Ag75(PET)40 [ii], ∼Ag114(PET)46 [iii], Ag152(PET)60 [iv], ∼Ag202(BBS)70 [v], ∼Ag423(PET)105 [vi], and
∼Ag530(PET)100 [vii]. (b) UV/vis spectra of clusters with wavelength on the x-axis. From bottom to up: Ag44 [i], Ag55 [ii], ∼Ag75 [iii], ∼Ag114 [iv],
Ag152 [v], ∼Ag202 [vi], ∼Ag423 [vii], ∼Ag530 [viii], and AgNPs [ix]. The spectra show multiple features up to [iv] (namely, eight bands for Ag44, two
energy bands for Ag55 and ∼Ag114, and three for ∼Ag75). But from [v] to [ix], only a single plasmon-like feature was observed with a small blue shift
(i.e., at higher energy). All the spectra have been shifted vertically for clarity. Reprinted with permission from ref 194. Copyright 2014 Royal Society
of Chemistry.

Au130.324 More information about the crystal structures of silver temperature dependency of the Au25(SR)18 cluster in terms of
clusters is presented in Table 3. its optical and photoluminescence properties. Thermal
4.5. Thermal Stability of Silver Clusters desorption of monolayer protected gold clusters results in the
Thermal stability of monolayer protected clusters is an formation of alkyl disulfide in the gas phase and gold in the
important property to explore. We have already discussed the solid state.461 The Au−S bond in several self-assembled
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Figure 18. (a) Chromatograms of PdAu24(SC12H25)18−n(SBB)n (n = 6−16) at different gradient programs. (b and c) Comparative MALDI mass
spectra in negative mode (b) and chromatogram (c) of PdAu24(SC12H25)18−n(SBB)n (n = 6−16) obtained using a gradient program [40],
respectively. Reprinted from ref 12. Copyright 2013 American Chemical Society.

monolayers was seen to be stable even at temperatures in the ∼Ag423(PET)105, and ∼Ag530(PET)100468 were prepared and
range 100−150 °C.462−465 This stability has also been observed characterized using MALDI MS (Figure 17a).194 Up to ∼Ag114,
for silver clusters.466 Remya et al.461 illustrated the thermal multiple features were seen in the UV/vis spectra of the
stability of atomically precise silver clusters protected with clusters. For Ag152 and clusters larger than that, the plasmonic
glutathione. With increase in temperature, the clusters feature corresponding to a single peak at ∼460 nm evolved
underwent thiolate desorption as well as heterolytic bond pointing to the emergence of metallicity in clusters composed
cleavage, resulting in the formation of Ag2S nanoparticles at 80 of ∼150 metal atoms (Figure 17b).194 For silver clusters,
°C. The cluster initially dissociates into thiolates (AgSR) which metallicity has been seen at about 60 atoms (in unprotected
can have the following two possible cleavage mechanisms. clusters) in photoelectron spectroscopic studies, as mentioned
by Taylor et al.469 These photoelectron spectroscopic studies
2R−S−Ag → 2Ag + R−S−S−R (8) are generally discussed in the light of initial and final state
effects.469 Systematic shift of the 4f binding energy has been
2R−S−Ag → 2Ag 2S + R−S−R (9) observed in supported gold clusters, but no such effect was
Out of these, reaction 9 was seen thermodynamically observed in supported silver clusters.469 The “spherical shell
favorable as ΔH is more negative.461 It is interesting to note model”104 suggests that the change in ionization energy as well
that this is much lower than the temperature (∼200 °C) as the increased width of the photoelectron spectra is
needed for traditional Ag2S nanoparticle synthesis. The proportional to 1/R, where R is the radius of the cluster.
mechanism of formation of Ag2S nanoparticle by this route However, naked clusters have been used in all of these
and its detailed characterization have been explored. The S−C photoelectron spectroscopic experiments, whereas this study
bond cleavage, as revealed by mass spectrometry, in silver has used monolayer protected clusters with distinct cores of
clusters is somewhat unusual because Ag−S cleavage is smaller dimensions. Clusters with different ligands such as BBS
expected in view of its lower bond energy. In another study, also showed this, which implies that “the emergence of
Bakr et al.450 have shown nonplasmonic to plasmonic metallicity” is independent of the functionality of the thiol
transformation of monolayer protected silver clusters ligand.194
(IBANs) at ∼90 °C. Several factors such as heat, light, etc.,
affect the stability of silver clusters, as silver is easily oxidized 5. CHEMISTRY OF CLUSTERS
under these conditions. In view of this, thermal desorption of Additional functionalization of the shell (i.e., ligands) of the
monolayers results in unprotected clusters, which have been monolayer protected clusters can introduce new and diverse
used for catalysis. It is a standard practice to store such clusters properties in such systems which may be important in different
in argon or nitrogen atmosphere in a refrigerator. applications. Some of these aspects are described below.
4.6. Emergence of Metallicity in Silver Clusters 5.1. Ligand Exchange
The plasmon resonance which is defined as a strong collective Ligand exchange is the most suitable and convenient way to
oscillation of electrons467 is responsible for the optical features incorporate desired properties such as FRET, chirality, etc., in a
and colors of noble metal nanoparticles. Several techniques given monolayer protected noble metal cluster.283,470−472 The
such as photoelectron spectroscopy, conductivity, etc., are used sole idea of ligand exchange is to keep the cluster core intact
to understand the emergence of metallicity in bare metal while modifying the shell. This strategy was originally utilized
systems. Chakraborty et al. have demonstrated the emergence by the Hutchison group473,474 to replace the phosphine ligands
of metallicity in monolayer protected silver clusters through of undecagold clusters by thiolate without changing the core
optical spectroscopy.194 A systematic appearance of a plasmon- size. The Pradeep group has also shown several exchange
like optical absorption feature as a function of cluster size was possibilities and incorporation of diverse properties in the Au25
observed in these systems. A wide range of clusters, namely cluster.283,475,476 However, ligand exchange can result in an
Ag44(4-FTP)30,30 Ag55(PET)31, ∼Ag75(PET)40,11 increase of the core size as was demonstrated by Shichibu et
∼Ag114(PET)46, Ag152(PET)60,16 ∼Ag202(BBS)70, al.477 for Au11 cluster; whose ligand exchange led to the
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Figure 19. (a) Scheme of the intercluster reaction to yield alloy clusters. (b) Negative ion mode MALDI MS spectra showing time dependent
changes in the reaction mixture of Au25(FTP)18 and Ag44(FTP)30 after 1 (i) and 3 h (ii) of the reaction. [Au21−xAgx(FTP)14] are fragments from the
alloy clusters due to the loss of Au4(FTP)4. Reprinted from ref 233. Copyright 2016 American Chemical Society. (c) (i) Minimum energy
configuration of the adduct, Au25(PET)18−Ag25(DMBT)18 (II−I) upon intercluster reaction. Dashed lines show the shortest distances found
between atoms in the staples of the two clusters which are marked with letters A−D on I and E−I on II. The hydrogen atoms are omitted from the
ligands for clarity. Color code for the atoms: Au (red), Ag (green), S (yellow), and C (blue). (ii) Full range ESI MS spectrum of the mixture of
Ag25(DMBT)18 (I) and Au25(PET)18 (II) at molar ratio (I:II) of 0.3:1.0 measured immediately after mixing. Inset a′ shows a feature due to the
dianionic adduct, [Ag25Au25(DMBT)18(PET)18]2− formed between I and II. Theoretical (blue) and experimental (red) isotope patterns of the
adduct features are given in the inset b′. Reprinted with permission from ref 310. Copyright 2016 Nature Publishing Group.

formation of the most stable Au25 cluster. Niihori et al.12 have 18b) also shows an envelope similar to that of the HPLC
shown the precise isolation of ligand exchanged clusters taking chromatogram (Figure 18c). Each of these clusters was isolated
PdAu24(SR)18 as an example. Each individual species of
and characterized using MALDI MS. Recently, the authors have
composition PdAu24(SR1)18−n(SR2)n (n = 0, 1, 2, ..., 18) was
isolated using gradient HPLC. The corresponding chromato- carried out an extensive study of the separation and isolation of
grams are displayed in Figure 18a. The mobile phase was alloy clusters, such as Au24Pd(SR1)18−x(SR2)x and Au24Pd-
systemically varied from pure MeOH to THF. The numbers 10,
(SR1)18−x(SeR2)x (SR1, SR2 = thiolate; SeR2 = selenolate).256
20, 30, 40, and 50 in Figure 18a refer to the time (in minutes)
taken for the mobile phase to become 100% THF, starting from Precise isolation after ligand exchange reaction opens up the
pure MeOH. The corresponding mass spectral feature (Figure possibility of individual structure analysis of clusters.
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5.2. Ligand Conjugation Formation of such an adduct is highly unlikely considering the
Ligand conjugation creates new properties such as fluorescence negative charge of clusters, but in this case, the charge is well
resonance energy transfer (FRET) in the cluster system. dispersed which does not create significant repulsion between
Muhammed et al.478 incorporated the dansyl group in each other. The van der Waals attractive forces between the
Au25(SG)18 cluster through ligand conjugation, which led to alkyl/aryl groups in the staple motifs are responsible initially
the observation of FRET in the conjugated cluster. Au25(SG)18 (Figure 19c,ii) for the formation of such adducts as confirmed
shows an emission at 585 nm (corresponding to an excitation form the molecular docking simulations. These two reports of
of 535 nm), which overlaps with the emission band (peak intercluster reactions suggest that clusters can be treated exactly
maximum at 505 nm) of the dansyl chromophore. As a result, like molecules; they can exchange atoms without structural
excitation of the dansyl group at 303 nm generates FRET. A deformation. Baksi et al. discovered the gas phase dimer of
systematic quenching of dansyl’s emission and increase in Au25(SR)18 using ion mobility mass spectrometry.480 Such
emission intensity of Au25(SR)18 cluster suggests FRET, and it transient species are shown to be important in explaining the
is generated through the energy transfer from the dansyl chemical reactivity between clusters.
chromophore to the Au25(SR)18 cluster. A glutathione
6. ALLOY CLUSTERS
protected silver cluster has been functionalized with graphene
through ligand conjugation.54 This interesting behavior of Bimetallic nanostructures,481 especially clusters, are of tremen-
ligand conjugation presents the probability of a new class of dous interest, particularly in the field of catalysis, because of
quantum cluster systems. their distinct properties from their corresponding monometallic
counterparts.482 Doping can also improve the cluster stability.
5.3. Intercluster Reactions The very first example of an atomically precise bimetallic
Krishnadas et al.233 have shown mass spectrometric inves- cluster, PdAu24(SR)18, was synthesized by the Murray group,303
tigations of intercluster reaction between Au25(SR)18 and which was further examined by the Negishi and Tsukuda
Ag44(SR)30 (a schematic of which is shown in Figure 19a) for groups198,483 in greater detail. Negishi et al. performed the
the first time creating alloy clusters. Under ambient conditions, HPLC technique to isolate the cluster with high purity.198
these clusters undergo spontaneous reactions in solution to Figure 20a shows the MALDI MS of the isolated PdAu24(SR)18
form alloys, preserving the M25 and M44 nuclearity. The
product peaks were distributed mainly in two regions: one near
Au25(PET)18 peak regions (group I) and the other one near
Ag44(FTP)30 peak regions (group II). HRESI MS of the
reaction mixtures with different cluster ratios show (Figure
19b) different branches of peaks (in the group I regions). Two
kinds of mass difference, corresponding to 89 and 99 Da, were
seen which are due to exchange of Ag−Au and (Au−PET)−
(Ag−FTP), respectively. Based on the HRESI MS data, the
series of peaks in group I were assigned with the general
formula, Au25−xAgx(PET)18−y(FTP)y. With increase in the
concentration of Ag44(FTP)30 in the reaction mixture,
incorporation of more Ag and FTP ligands in Au25(PET)18
was noticed. Inclusion of Ag was seen from 1 to 13. Metal Figure 20. (a) Negative-ion MALDI mass spectra of fractions 2 (Au25
inclusion alone is noticeable when same ligands are used for cluster) and 3 (PdAu24 cluster) separated by HPLC. Reprinted with
both clusters. MALDI MS data of the reaction products permission from ref 198. Copyright 2010 Royal Society of Chemistry.
between the FTP protected Au25 and Ag44 cluster are presented Inset shows the recent crystal structure of Au24Pd(PET)18. Reprinted
in Figure 19c, which clearly confirm the formation of from ref 484. Copyright 2016 American Chemical Society. On the
Au25−xAgx(FTP)18 clusters. Silver inclusion of 1−5 atoms right side, (b), (c), and (d) are the crystal structures
(Figure 19b,i) and 1−13 atoms (Figure 19b,ii) were seen after [Au13Cu2(PPh3)6(SPy)6]+ (Py = 2-pyridyl), PdAg24(2,4-SPhCl2)18,
1 and 3 h of reaction, respectively. Interestingly, after 24 h of and [Ag46Au24(SR)32](BPh4)2, respectively. (b) Reprinted from ref
488. Copyright 2013 American Chemical Society. (c) Reprinted from
reaction, Ag inclusion of up to 17 atoms was noticed. This ref 489. Copyright 2015 American Chemical Society. Reprinted with
report shows the role of metallic core and the surrounding permission from ref 490. Copyright 2015 American Association for the
monolayers in determining the chemistry of these clusters. Advancement of Science.
Zhang et al.479 have shown that Ag migration takes place
between Au38(PET)24 and doped AgxAu38−x(PET)24 clusters in
solution. Collisions between the reacting clusters are the reason cluster and its monometallic analogue Au25(SR)18, which differ
for such a migration. by 91 mass units. From a detailed structural analysis, it was
In a recent report, Krisnadas et al. have found that the inferred that the Pd atom sits in the central position of the
reaction of Au25(SR)18 cluster with corresponding silver icosahedral core and that the alloy cluster has an enhanced
analogue, Ag25(SR)18, produced (Figure 19c,i) AgmAun(SR)18 stability compared to the Au25(SR)18 cluster. The position of
clusters (n = 1−24; m + n = 25), keeping the structure intact.310 Pd was further confirmed from the recent crystal structure of
This is basically a substitution reaction where one cluster Au24Pd(SR)18 cluster (inset of Figure 20a).484 Similarly, Ag,485
converts to another without changing the structure, as both Cu,197,486 Pt,199 Cd,19 and Hg19 doped Au25 and alloy clusters
Au25(SR)18 and Ag25(SR)18 have the same structure. A of three different metals, with the general formula
dianionic adduct, which was believed to be the earliest M1AgxAu24−x(SR)18487 (where M = Cd, Hg), have also been
intermediate in such reactions, has been detected in electro- reported by different research groups.491 A few examples of
spray ionization mass spectrometry (inset of Figure 19c,i). alloys of other stable gold clusters, such as Au38492,493 and
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Chemical Reviews Review

Au144,494 are also there in the literature. Udayabhaskararao et ing.389,396,398,503−506 Especially, using BSA, several atomically
al.17 synthesized the Ag7Au6 alloy cluster from Ag7,8 clusters on precise clusters such as Au8@BSA,371 Au16@BSA,504 Au38@
successive addition of Au3+ solution. The alloy showed BSA,507 Ag8@BSA,508 Ag15@BSA,32 Ag31@BSA,509 etc., have
enhanced luminescence, both in the solution and in powder been made.370,383,396,399,503−505 Different proteins such as
form. The excitation and emission features changed from 670 lysozyme,401,510−512 lactotransferrin,214,371,513 insulin,514,515
to 390 nm and from 770 to 650 nm, respectively relative to the pepsin,516 trypsin,517 etc., have been used as scaffolds to
monometallic clusters. Similarly, differences in the absorption synthesize a variety of metal and alloy nanoclusters. Chaudhari
features are also expected. Biltek et al. proposed a structure for et al. have tried to understand the evolution and growth of
the bimetallic Ag4Ni2(DMSA)4 cluster using calculations.495 nanoclusters inside protein templates using MALDI MS
Yang et al. reported the crystal structures of three alloy clusters, analysis.371 They have also investigated the kinetics of the
Au13Cux (x = 2, 4, 8), and for x = 2, the structure has been cluster growth by monitoring the fluorescence intensity.518 Size
presented in Figure 20b.488 The structure contains an Au13 evolution of protein protected clusters has also been
icosahedron which is passivated by six PPh3 and six 2- investigated by small-angle X-ray scattering (SAXS).519 Because
pyridinethiolates. Each Cu is coordinated by three pyridyl of their biocompatibility, they have been used in several
groups and they are face-capped. Au12Ag32(SR)30 has a applications and many of them have been discussed in the
structure similar to the Ag44(SR)30 cluster with 12 gold atoms application section.378,379,390,504,505,520−522 Many review ar-
replacing the silver atoms in the hollow cage,222 whereas the ticles50,52,55,523,524 and book chapters525,526 including some
recently discovered Ag−Cu alloy cluster [Ag28Cu12(SR)24]4− from the present authors have covered this topic in detail.
has a two-shell Ag4@Ag24 core protected by four nearly planar
Cu3(SR)6 moieties.496 Recently, crystal structures of alloys of 8. OTHER PROPERTIES
Ag25(SR)18 with Au,26 Pd (Figure 20c),489 and Pt489 have been
revealed. These heteroatoms are present at the center of the Along with their unique optical and photoluminescence
icosahedra, forming a general M@Ag12@Ag12(SR)18 structural characteristics, monolayer protected clusters exhibit some
configuration. Bootharaju et al. have shown unusual metal other properties such as two-photon absorption, optical
exchange pathways for MAg24(SR)18 clusters (where M = Pd, nonlinearity, magnetism, etc. These are briefly discussed in
Pt).497 The central Pd atom of [PdAg24(SR)18]2− cluster was sections 8.1 and 8.2.
replaced by Au during the metal exchange process to produce a 8.1. Two-Photon Absorption
bimetallic [AuAg24(SR)18]− cluster along with a minor product Optical nonlinearity is a remarkable property270,527−531 of
of [Au2Ag23(SR)18]−, whereas the central Pt atom remained noble metal clusters. The nonlinear optical (NLO) properties
intact in [PtAg24(SR)18]2− clusters.497 In this case, the incoming include two-photon absorption (TPA),532,533 two-photon
gold replaced the noncentral Ag atoms to form trimetallic fluorescence (TPF), and second/third harmonic generation
[AuxPtAg24−x(SR)18]2− NCs, with x = 1−2. Wang et al. have (SHG/THG).528,529 The simultaneous absorption of two
reported the single crystal structure of [Ag46Au24(SR)32]- photons (of identical or different frequencies) in order to
(BPh4)2 (Figure 20d) which also shows enhanced catalytic excite a molecule from the ground state to a higher energy
activity.490 The structure can be represented simply as Ag2@ electronic state is often known as TPA. Ramakrishna et al.534
Au18@Ag20@Ag24Au6(SR)32. This is the very first alloy cluster observed a similar phenomenon for Au25(SR)18 clusters. This
with gold and silver coexisting on staples. Similarly, a recent cluster can be useful for two-photon imaging with infrared light
report of [Au80Ag30(CCPh)42Cl9]Cl cluster can be presented as it has reasonable luminescence efficiency (∼2.5 × 10−4) in
as Au6@Au35@[email protected] More information about the NIR region. Figure 21a shows the corresponding optical
alloy clusters reported so far is given in Table 4. spectrum of Au25 cluster protected with hexanethiol (taken in
hexane solvent). As discussed earlier, it consists of several bands
7. PROTEIN PROTECTED CLUSTERS starting from the ultraviolet to the visible region with a
Similar to several ligands, proteins can also act as stabilizers and maximum near 675 nm. Excitation at 1290 nm from the output
a few proteins also have the added advantage of reducing of an optical parametric amplifier results in emission with a
power, using which they can reduce the precursor metal ions of maximum at 830 nm (Figure 21a). Slope from the
Au, Ag, Cu, etc. Even though formation of nanoparticles corresponding pump-power dependency plot (Figure 21b)
through proteins was easy and efficient, controlling the size to gave a value of ∼2 which indicates that it is a two-photon
make atomically precise nanoclusters with proteins was not excited emission. Using H2TPP in toluene as standard, the TPA
attempted until 2009. Xie et al. have succeeded in synthesizing cross section for Au25(SR)18 cluster was measured to be 2700
atomically precise Au25 cluster within the bovine serum albumin GM, which is superior to many other NIR emitting organic
(BSA) template.213 The synthetic methodology was very simple chromophores. The study also revealed that emission in the
which involved the mixing of Au3+ ion precursor with the visible region (maximum at 510 nm) is also a two-photon-
protein at alkaline pH.213 Under basic conditions, aromatic absorption phenomenon (Figure 21c,d). Patel et al.535
amino acids present in the BSA donate electrons to reduce the determined a large two-photon cross section value of ∼5000
gold ions while cysteine residue takes the place of the stabilizer GM for three water-soluble silver clusters emitting at 660, 680,
to form the Au nanocluster. Comparing the mass of Au@BSA and 710 nm, respectively. Two-photon excited fluorescence
cluster and that of BSA protein alone through MALDI MS, the from a DNA-templated Ag nanocluster has been reported by
number of Au atoms in the cluster can be calculated. From the Yau et al.536 Upon excitation of 800 nm, the cluster exhibited
mass spectral analysis, the number of Au atoms inside a BSA an emission at 630 nm with a two-photon-absorption cross
protein was found to be 25.213 Much higher QY (6%) was seen section of ∼3000 GM.
for this Au25@BSA cluster in comparison to the thiolated Au25 It is important to mention that, in most of the cases, the
cluster.213 After the pioneering discovery of this green route, multiphoton absorption and emission of nanoclusters have
many reports with new synthetic routes started evolv- been investigated at single wavelengths, which presents only a
8234 DOI: 10.1021/acs.chemrev.6b00769
Chem. Rev. 2017, 117, 8208−8271
 Table 4. List of Selected Alloy Clusters
physical
state of the
core ligand composition focus synthesis product other measured properties ref
Ag7Au6 mercaptosuccinic acid Ag7Au6(H2MSA)10 characterization three step solu- solid ESI MS, TDDFT, XPS, SEM/ 17
tion phase EDAX, 1H NMR, UV/vis
Au25−nAgn dodecanethiol Au25−nAgn(SC12H25)18 characterization Brust method solid MALDI MS, LDI, XPS, UV/vis 485
Chemical Reviews

Au24Pd phenylethanethiol PdAu24(PET)18 characterization Brust method solid ESI MS, ESI-FTICR-MS, MALDI 303
MS, AAS
Au24Pd dodecanethiol Pd1Au24(SC12H25)18 characterization Brust method solid HPLC, TGA, MALDI MS, XPS, 198
FT-IR, UV/vis
Au24Pt phenylethanethiol PtAu24(PET)18 characterization Brust method solid ESI-MS, UV/vis, SEC, 1H NMR, 199
COSY, XRD, MALDI MS
Au24Pt phenylethanethiol PtAu24(PET)18 structure and Brust method solid EXAFS, MALDI MS, XPS, calcu- 499
electronic prop- lation
erties
Au24Cd, phenylethanethiol CdAu24(PET)18, HgAu24(PET)18 crystal structure, Brust method solid ESI MS, UV/vis, TGA, MALDI 19
Au24Hg properties with modifica- MS, TDDFT
tion
Au25−nCun octaneselenol CunAu25−n(SeC8H17)18 (n = 0−9) characterization modified Brust solid MALDI MS, UV/vis, DPV, PL, 197
method XRD and TEM
Au25Ag2 phenylethanethiol Au25Ag2(PET)18 characterization solution phase solid UV/vis, ESI MS, DFT, XRD, 500
mixing catalysis
Au24Pd, phenylethanethiol PdAu24(PET)18, PdAu37(PET)24, characterization modified Brust solid MALDI MS, UV/vis, SEC, LDI 492
Au37Pd, Pd2Au36(PET)24 method
Au36Pd2

8235
Au36Pd2 phenylethanethiol Pd2Au36(PET)24 characterization modified Brust solid HR ESI MS, MALDI MS, XPS 493
method
(Au−Ag)144 phenylethanethiol (Au−Ag)144(PET)60 characterization modified Brust solid UV/vis, ESI MS, MALDI MS, 494
method
Ag4Ni2 dimercaptosuccinic acid Ag4Ni2(DMSA)4 characterization one step solution solid ESI MS, UV/vis, PAGE, calcula- 495
phase tion
Au13Cux(x = 2, pyridine-2-thiol, 4-tert-butylbenzenethiol, triphenylphosphine, pyridinediphe- [Au13Cu2(PPh3)6(SPy)6]+, crystal structure two step solution solid UV/vis, computational calcula- 488
4, 8) nylphosphine [Au13Cu4(PPh2Py)4(SC6H4-tert- phase tion, TGA, ESI MS, and cata-
C4H9)8]+, [Au13Cu8(PPh2Py)12]+ lytic performance
Au12Ag32 p-fluorothiophenol, 3,4-difluorothiophenol, 4-(trifluoromethyl)thiophenol Au12Ag32(SR)30 crystal structure one step solution solid UV/vis, PDOS, calculation 222
phase
Ag28Cu12 2,4-dichlorobenzenethiol [Ag28Cu12(SR)24]4− crystal structure one step solution solid UV/vis, ESI MS, CD, DFT 496
phase
Au24Ag20 phenylalkynyl, 2-pyridylthiolate Au24Ag20(2-SPy)4(PhCC)20Cl2 crystal structure two step solution solid UV/vis, TGA, TPD MS, PDOS 501
phase
MxAu25−x phenylethanethiol CuxAu25−x(SR)18, AgxAu25−x(SR)18, characterization solution phase solid ESI MS, UV/vis, MALDI MS 502
Cd1Au24(SR)18 and Hg1Au24(SR)18 and crystal
structure
M1AgxAu24−x phenylethanethiol Cd1AgxAu24−x(SR)18, characterization solution phase solid ESI MS, UV/vis 487
Hg1AgxAu24−x(SR)18
Ag24Au dimethylbenzenethiol AuAg24(SPhMe2)18− crystal structure solution phase solid ESI MS, UV/vis, transient ab- 26
then galvanic sorption
exchange
Ag24Pd, Ag24Pt 3,5-dichlorobenzenethiol (PPh4)2[PdAg24(SR)18], crystal structure solution phase solid ESI MS, UV/vis, CD, TGA, DFT 489
(PPh4)2[PtxAg25−x(SR)18] (x = 1, 2)
Ag46Au24 tert-butylthiol [Ag46Au24(SR)32](BPh4)2 crystal structure solution phase solid NMR, TEM, UV/vis 490
Review

Au80Ag30 phenylalkyne [Au80Ag30(CCPh)42Cl9]Cl crystal structure solution phase solid UV/vis 498

DOI: 10.1021/acs.chemrev.6b00769
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Chemical Reviews Review

Figure 21. (a) Optical absorption of Au25(SR)18 cluster and two-photon emission spectrum after excitation at 1290 nm. (b) Power dependence of
the fluorescence obtained at 1290 nm suggesting it to be a two-photon process. (c) Two-photon excited fluorescence spectra of Au25(SR)18 at
different pump powers after excitation at 800 nm and (d) power dependence of the emission at 510 nm. Reprinted from ref 534. Copyright 2008
American Chemical Society.

fragmentary image of the NLO properties. Recently, Olesiak- which revealed that the unpaired spin resides in the HOMO
Banska et al.533 have investigated third-order NLO properties that has a distinct p-like character (Figure 22). This switching
of Au25(Capt)18 clusters by the Z-scan technique with property of the Au25(SR)18 cluster can therefore be used as a
femtosecond laser excitation in a broad range of wavelengths. paramagnetic probe. Negishi et al.539 investigated a series of
They have also listed a summary of NLO properties of gold atomically precise clusters of general formula AuN(SG)M, where
nanoclusters reported so far.533 (N, M) = (10, 10), (15, 13), (22, 16), (22, 16), (25, 18), (29,
8.2. Magnetism 20), and (39, 24), by studying them via X-ray magnetic circular
dichroism. The magnetic moment was found to increase with
Single gold atoms (adsorbed on a support or in gas beams) are increase in the cluster core size. The hole created by Au−S
paramagnetic, whereas bulk gold is diamagnetic.352 The bonding was more responsible than the quantum size effect of
paramagnetism is due to the unpaired 6s electron of gold. gold clusters, for the spin polarization phenomenon. McCoy et
Such paramagnetism and its evolution from single gold atoms al.540 have shown that chemical oxidation can lead to
to metallic nanoparticles are of potential interest and superatom paramagnetism in Au102(MBA)44 cluster. The
importance in the understanding of the magnetic nature of superatom electron configuration of Au102(MBA)44 cluster is
gold. Hori et al.537 reported size dependency of magnetism of (1S)2 (1P)6 (1D)10 (2S)2 (1F)14 (2P)6 (1G)18. Addition or
gold nanoparticles; they claimed that thiol suppresses magnet- removal of electrons from these superatomic orbitals can make
ization. In 2005, Crespo et al. showed the magnetism in the superatom a paramagnet.
thiolated nanoparticles of 1.4 nm.538
Similarly, the magnetic nature of gold clusters, especially 9. APPLICATIONS
when they are atomically precise, needs to be investigated. Zhu
The unique optical and luminescence properties of noble metal
et al. 352 found reversible switching of magnetism in
nanoclusters make them highly appropriate for various
Au25(PET)18 cluster. The EPR spectra of microcrystalline and
applications such as sensing,541,542 catalysis,543,544 optics,
frozen solutions of [Au25(SR)18]0 cluster showed an S = 1/2
imaging,50 and biolabeling.3,53,55,162,298,510,545−548 Mathew and
signal, which suggests that each cluster has one unpaired spin.
Pradeep51 have addressed the applications of noble metal
The EPR signal disappeared upon the reduction of the cluster
nanoclusters in detail in their review article. Some specific
to its negative charge state, [Au25(SR)18]−. Interestingly, the
examples are explained below.
signal could be switched back when the negatively charged
cluster was oxidized using H2O2, to return back to the neutral 9.1. Sensors
cluster. Thus, paramagnetism could be switched on and off just Sensing of different molecules or biomolecules or ions
by changing the charge state of the cluster (Figure 22). The including hazardous ions (such as Hg2+) using nanomaterials
origin of this magnetism was explained by DFT calculations, have now become an interesting topic in materials
8236 DOI: 10.1021/acs.chemrev.6b00769
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Chemical Reviews Review

change in the color of luminescence. Initially, fluorescent

isothiocyanate (FITC) was coated on the gold mesoflowers,
which resulted in bright green luminescence. Further
functionalization with Ag15@BSA cluster on the Au@SiO2−
FITC mesoflowers produced red luminescence (Figure 23a).
Upon exposure to Hg2+ or TNT (trinitrotoluene), the red
luminescence was quenched and a green luminescence,
characteristic of the underlying FITC, appeared. In some
instances, sensing is based on fluorescence enhancement
(details are given in Table 5). Most of the literature on sensors
is focused on the detection of Hg2+ and Cu2+ ions. For example,
gold clusters have a strong tendency to sense Cu2+, as can be
seen from the case of Au15 clusters reported by Shibu et al.555
This cluster was fabricated with chitosan to make a composite
whose intense red luminescence (Figures 23b,c) was quenched
upon addition of Cu2+ or on dipping the composite in Cu2+
solution.552 The composite film exhibited visual sensitivity to
Cu2+, up to 1 ppm (Figure 23d), below the permissible limit
(1.3 ppm) in drinking water (by the Environmental Protection
Agency (EPA)). Although the limit of detection for toxic metal
ions reached below the parts per billion level in a few
reports,511,556 the underlying mechanism was not identified.
The luminescence and optical properties of noble metal
nanoclusters are highly sensitive to the local environment and
Figure 22. (a) Reversible conversion between neutral and anionic depend on the interaction with external analytes, which makes
Au25(SR)18 nanoparticles. (b) DFT-calculated Kohn−Sham orbital these clusters act as “turn-off” or “turn-on” sensors.49 Since
energy level diagrams for neutral and anionic nanoparticles,
respectively. (c, d) Views of the Kohn−Sham HOMO for
these clusters have a core−shell geometry, the analyte can
[Au25(SH)18]0 at LB94//XR/TZP level of theory. The HOMO interact with the metal atoms in the core as well as with the
possesses two lobes and exhibits distinct P-like character. Image d is ligands forming the shell. There are three types of primary
rotated relative to (c) to show one of the lobes (contributed by three interactions between metallic core and analytes, namely (i)
Au atoms in the icosahedral shell). Color code: purple, Au; yellow, S; analyte induced metal core decomposition, (ii) deposition of
white, H. Reprinted from ref 352. Copyright 2009 American Chemical analyte on the metal surface, and (iii) metallophilic interactions.
Society. Interaction with the shell can take place by (i) an enzymatic
reaction, (ii) incorporation of recognition moieties, or (iii)
science.545,547,549−551 Noble metal nanoclusters have also begun analyte induced aggregation.49 As an example, a mechanism has
to play an important role in this regard.216,547,552,553 In most of been outlined to describe the interaction of Hg2+ with
the cases, luminescence quenching is primarily utilized. Mathew luminescent silver clusters.216 It was proposed that the
et al.554 developed a novel sensor based on a hybrid material, interaction is induced by the ligands that contain thiol moieties.
composed of two systems, namely, gold mesoflowers and BSA Because of the soft−soft interaction with S, Hg2+ initially gets
protected Ag15 clusters. Here, too, the sensing indicator was the attached to the ligand and then sits on the silver surface where

Figure 23. (a) Schematic of different analytes sensing by Ag15 cluster coated gold mesoflower. Reprinted with permission from ref 554. Copyright
2012 John Wiley & Sons. (b and c) Photographs of Au15 cluster incorporated film under white light and UV light, respectively. (d) Dependence of
Cu2+ concentration on luminescence quenching. Reprinted from ref 552. Copyright 2012 American Chemical Society.

8237 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
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Table 5. Sensing Properties of Metal Clusters

sensed metal ion/ property with which sensing was
sensor type cluster core protecting ligand molecule done sensing limit ref
chemical sensor Agn glutathione Hg2+ absorption and fluorescence 1 ppb 216
quenching
Ag4,5 lipoic acid Hg2+ fluorescence quenching 10−10 M 212
Aun BSA Cu2+ fluorescence quenching 5 × 10−5 M 520
Au15 GSH and cyclodextrin Cu2+ fluorescence quenching 1.3 ppm 552
Aun lipoic acid Hg2+ fluorescence quenching 5 × 10−10 M 294
Agn denatured BSA Hg2+ fluorescence quenching 1 × 10−8 M 557
Au38 BSA Cu2+ fluorescence quenching 1.5 × 10−8 M 507
Au10−39 glutathione Cu2+ fluorescence quenching 8.6 × 10−8 M 558
Aun 11-mercaptoundecanoic Hg2+ fluorescence quenching 5 × 10−9 M 559
acid
Aun lysozyme Hg2+ fluorescence quenching 3 × 10−12 M 511
Aun thiolate α-cyclodextrin Hg2+ fluorescence quenching 4.9 × 10−11 M 556
Aun lysozyme Hg2+ fluorescence quenching 1 × 10−8 M 510
Aun BSA Hg2+ FRET 1 × 10−10 M 560
Aun BSA Hg2+ fluorescence quenching 5 × 10−10 M 561
Aun glutathione Cu2+ fluorescence quenching 3.6 × 10−9 M 562
Agn polymethacrylic acid Cr3+ fluorescence quenching 1 × 10−7 M 563
Au16 BSA Ag+ fluorescence enhancement 1 × 10−7 M 504
Au25 glutathione Ag+ fluorescence enhancement 2 × 10−7 M 504
Aun BSA CN− fluorescence quenching 2 × 10−7 M 564
Ag14 glutathione S2− fluorescence quenching 2 × 10−9 M 302
Aun oligonucleotide Hg2+ fluorescence quenching 5 × 10−9 M 565
Aun BSA Hg2+ fluorescence quenching 80 nM 521
Aun cysteine As3+ fluorescence quenching 53.7 × 10 −9 M 566
Cu5 and Cu13 BSA Pb2+ fluorescence quenching >20 ppm 522
Agn polymethacrylic acid Cu2+ fluorescence quenching 8 × 10 −9 M 567
Aun Nlf Cu2+ fluorescence quenching 10 ppm 214
AgAu BSA Al3+ fluorescence quenching 0.8 × 10 −6 M 568
biological sensor Aun PAMAM hIgG turn-off fluorescence mM to nM 569
Agn DNA miRNA turn-off fluorescence 0.5 × 10−6 M 570
Aun MUA PDGF AA turn-on fluorescence 0.5 × 10 −9 M 571
Aun S-mannose Con A turn-off fluorescence 75 × 10−12 M 572
Aun mannose Tg turn-on fluorescence 48 × 10−12 M 573
Aun S-mannose Tg turn-on fluorescence 90 × 10−12 M 574
Aun and AuNPs mannose, anti-Tg Tg turn-on fluorescence 65 (±16) × 10−9 M 573
Aun glutathione GST-tagged proteiens naked eye detection 750 × 10−9 M 575
Aun protein A hIgG turn-on fluorescence 10 × 10−9 M 576
Agn DNA-Apt thrombin turn-off fluorescence 1 × 10−9 M 577
Agn DNA human Braf oncogene turn-on fluorescence 10 × 10−9 M 217
∼Ag10 DNA DNA turn-on fluorescence <1 × 10−6 M 578

it oxidizes Ag(0) to Ag+ ion. In the process, Hg2+ gets reduced and, therefore, can easily get attached to the cluster core. Many
to its metallic state and forms an alloy with the silver core, examples of this kind are reported in the literature. For a
which has been probed by TEM and PXRD. Details of the detailed discussion, the readers may refer to the book chapter
limits of sensing of several ions are listed in Table 5. by Ackerson et al.588 Another property of gold nanoclusters
9.2. Biological Applications that has been used for biolabeling as well as bioimaging is
Because of the nontoxicity of gold particles, they have been fluorescence. Liu et al. have shown that insulin encapsulated
extensively used in various biological applications579 such as highly red luminescent Au nanoclusters can be used for
biolabeling,580 cancer treatment,581,582 drug screening,583 drug fluorescence imaging (Figure 24a).514 The initial target was to
delivery,580,584,585 etc.55,505,547,585−587 Silver clusters are mostly check the cytotoxicity, for which C2C12, a mouse myoblast cell
toxic for biological applications, as silver ions leach into the line, was used as a test candidate. The uptake efficiency of
cells and kill them completely above a threshold. Hence, they insulin−Au nanoclusters for C2C12 cells served as a biomarker
can only be used for limited imaging purposes and for their to distinguish the differentiated versus undifferentiated C2C12
antibacterial activity. Below is a discussion of a few biological myoblasts. The cells with suitable treatment were imaged under
applications of gold and silver clusters. a confocal microscope to examine the uptake of the insulin−Au
9.2.1. Biolabels. Cysteine with its thiol functionality can nanoclusters after 2 h of feeding. Color processing of the
easily coordinate with gold because of the strong binding obtained image was further carried out to make each
between gold and sulfur. This strategy has been used for compartment more distinguishable. The corresponding image
biolabeling as some proteins contain this amino acid residue is shown in Figure 24a, which clearly shows that the intense red
8238 DOI: 10.1021/acs.chemrev.6b00769
Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

Figure 24. (a) Microscopic observation of internalization of insulin−Au nanoclusters. Differentiated C2C12 myoblasts were treated with insulin−Au
nanoclusters for 2 h. (i) Cell nucleus stained with 4′,6-diamidino-2-phenylindole (DAPI, blue). (ii) Actin fiber stained with Alexa Fluor 488
phalloidin to confirm the cell boundary (green). (iii) Insulin−Au nanoclusters exhibit red luminescence. (iv) Fluorescence image overlay of the three
images. Reprinted with permission from ref 514. Copyright 2011 John Wiley & Sons. (b) Typical FLIM images of HeLa cells with internalized Au
nanoclusters at four different temperatures. Reprinted with permission from ref 589. Copyright 2013 John Wiley & Sons. (c) Bright-field (i, iii) and
corresponding fluorescence microscopy (ii, iv) images showing the interaction of FA-conjugated Au nanocluster@BSA with different types of cell
lines. Left panel (i and ii): images of folate-receptor-positive KB cells with FA-conjugated Au nanocluster@BSA incubated for 24 h; right panel (iii
and iv): images of folate-receptor-negative mouse fibroblast L929 cells with FA-conjugated Au nanocluster@BSA incubated for 24 h. Reprinted with
permission from ref 507. Copyright 2010 John Wiley & Sons.

fluorescence of insulin−Au nanoclusters overlap with that of 9.2.2. Biomedical Targeting. Integrating biocompatibility,
the fully differentiated C2C12 mouse myoblasts in the stability, low toxicity, and specificity of targeting desired organs
cytoplasm. and cells in a material or molecules is a great challenge in
Shang et al.589 demonstrated gold nanoclusters as biomarkers biology. Gold clusters have shown their effectiveness in this
for temperature sensing in human cancer cells. Incubation was field, too.548 Sun et al.591 have shown a controlled assembly of
done with Au nanoclusters in a serum-free cell culture medium paired gold clusters within an apoferritin reactor which can be
for 2 h. Appreciable amounts of Au nanoclusters were observed used for in vivo kidney targeting. Gold clusters were assembled
inside HeLa cells. Then, using a temperature controlled sample at the ferroxidase active sites of ferritin heavy chain. These
assembled clusters did not lose their intrinsic fluorescence
stage, the temperature of the environment of the HeLa cells
property, but rather underwent an enhancement. As a result,
was varied. Lifetime maps were calculated and are shown in these assemblies can also be used for in vitro and in vivo
Figure 24b, which provides clear evidence that the long imaging. Several other groups have used luminescent gold
fluorescence lifetime components in the range of 600−1000 ns nanoclusters as an effective targeting tool in biological
arise from the internalized Au nanoclusters rather than from the applications.384,548,592
cellular autofluorescence. Muhammed et al.22,507 have shown 9.2.3. Other Biological Applications. Noble metal
the biolabeling application effectively for BSA protected gold nanoclusters have been used in several other biological
clusters and the thiolated Au23 cluster. This gold nanocluster applications such as gene delivery,593 imaging,514,594,595
(BSA protected) is highly luminescent in the pH range 2−12, antibacterial activity,21,596 etc.548 In most cases, gold clusters
which makes it a good staining agent for cell imaging. It has two have been chosen because of their high biocompatibility and
advantages over quantum dots: low cytotoxicity and high low cytotoxicity, but silver shows higher antibacterial property
photostability. As certain cancerous cells (such as oral, ovarian, than gold.21 Silver ion leaching is the main reason behind their
and breast) are enriched with folic acid (FA) receptors and they antibacterial nature.
can internalize FA conjugated molecules, gold clusters have 9.3. SERS
been functionalized with FA by EDC coupling of FA and Surface enhanced Raman spectroscopy (SERS) of noble metal
BSA.590 This biolabeled nanocluster has been used for cancer nanoparticles,597−601 superlattices, or other nanostructures have
cell imaging, and it has been found that it can be an effective been studied extensively and various reports exist in the
tool to identify cancer cells as the bright red luminescence literature, but such reports are rare for ultrasmall nanoclusters.
(Figure 24c) appears only for clusters treated with cancer cells. Chakraborty et al. have shown SERS from an atomically precise
8239 DOI: 10.1021/acs.chemrev.6b00769
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Ag152(SR)60 cluster.602 Several analytes such as crystal violet polyvinylpyrrolidone (PVP) have high catalytic activity. From a
(CV), R6G, and adenine were used, and they exhibited effective detailed structural analysis using FTIR, XPS, and XANES, it
SERS on Ag152(SR)60 substrate with an enhancement factor of was found that these clusters were negatively charged. Thus,
the order 109. For CV, the lower detection limit was 10−9 M. PVP not only acts as a stabilizer but also modulates the
The cluster was drop cast on a glass slide, which was then used electronic structure that affects the catalytic activity. Several
as the SERS substrate. Plasmon-like optical features, crystalline oxidation reactions have been studied using these PVP
nature (of the individual nanoclusters and their assembly), and protected gold clusters656 whose details are summarized in
the absence of visible luminescence are the main reasons for Table 6.
this enhancement. It is noteworthy that this cluster can also be Supported heterogeneous catalysts have essentially two
coated on cotton and paper, and simultaneously its SERS can components: an active nanocluster and a support.659 Usually,
be measured. Unprecedented enhancement of Ag152(SR)60 metal oxides or other powders are used as supports. Anchoring
suggests a significant cost-saving associated with the use of the cluster on its surface to prevent sintering during catalysis is
these materials in comparison to typical silver nanoparticle the main role of the support. The preparation of such catalysts
systems composed of thousands of atoms. involves saturation of the metal oxide powder (support) in a
9.4. Catalysis cluster solution, followed by drying of the material and
Because of their high surface area, nanomaterials have proved to calcination at 350−1000 °C.659 At this high temperature, the
be effective in the field of catalysis.603−643 Additionally, noble protecting ligands get removed from the cluster system and the
metal nanoclusters have unique core−shell structures and bare clusters supported on the metal oxide are ready for
nonmetallic electronic properties which make them even more catalysis reactions. Such supported catalysts have shown high
attractive and promising in this area.644,645 Nanoclusters of size catalytic activities for a range of oxidation and epoxidation
1−2 nm exhibit strong quantum confinement effects that are reactions, as listed in Table 6.659 Turner et al.660 illustrated the
important for nanocatalysis. With precise composition and well- catalytic activity of Au55 cluster for the selective oxidation of
defined structures, it is indeed possible to correlate the styrene by dioxygen. They proposed that initially the gold
structural properties of these atomically precise entities with entities dissociatively chemisorb O2 to yield O adatoms, which
their catalytic properties. It is also possible to determine the trigger the subsequent catalytic chemistry. Au 11 , 661
active sites for the catalytic activity, which is important to Au25,361,662,663 Ag7,8,664 etc., also show catalytic activities
explore the chemistry of a catalyst. Among the noble metals, under different conditions and for different reactions. Xie et
gold shows enormous catalytic activity. Following the work by al. developed Au25 and PdAu24 cluster based catalysts supported
Haruta et al.646,647 on ultrafine gold particles smaller than 10 on multiwalled carbon nanotubes (Figure 26).663 Their study
nm, several studies investigated the catalytic activity of shows that single Pd atom doping can significantly improve the
gold. 6 4 8 , 6 4 9 The area has been reviewed previ- catalytic performance. Two possible mechanisms have been
ously.259,644,650−654 suggested for the Pd induced enhancement of catalytic
The novelty of such nanoparticles or nanoclusters lies in two performance. One could be the creation of highly active
major factors: (a) high enhancement in efficiency due to high reaction sites by the Pd atom on the surface of Au24, and the
surface to volume ratio and (b) extreme control over selectivity other is the activation of Au sites by Pd induced modulation of
by specific active sites. In general, there are two kinds of noble the electronic structure. Both of these mechanisms are well
metal particle catalysts: unsupported (Figure 25a) and supported, with two other reports for the case of Pd
incorporated gold particles665 and Au incorporated Pd
nanoparticles,666 respectively. But here authors support the
later one based on DFT structure analysis. As Pd atom was
located inside the Au icosahedron, DFT study predicts667 that
electron transfer occurs from Pd to Au. Therefore, based on
this structural model, Au sites in PdAu24@CNT are more
negative than Au25@CNT.
Electron transfer from Pd for the case of PdAu24@CNT
helps to activate the oxygen more effectively, which results in
increased catalytic performance compared to Au25@CNT.
Different groups659,668−676 have addressed several such
Figure 25. Schematic representation of homogeneous and heteroge- examples of catalytically active gold clusters in various articles
neous catalysis by gold cluster. (a) Oxidation reactions catalyzed by and reviews, and a brief summary is listed in Table 6.
Au@PVP clusters. (b) CO oxidation by Au25 cluster supported on a 9.5. Solar Cells
CeO2 surface.
Metal nanoclusters can also serve as effective photosensitizers
that can be used for designing solar cells.703 Chen et al.24
supported (Figure 25b). We will describe them briefly here, named such solar cells as metal cluster sensitized solar cells
although there are several review articles focusing on the (MCSCs). A glutathione protected gold cluster has been used
catalytic activity of noble metal nanoclusters.260,655−658 To as a sensitizer. The cluster shows bright orange luminescence
design a novel nanocluster catalyst, it is important for the (emitting at 600 nm), and it has an absorption feature near 400
cluster to have an exposed metal surface. As these clusters are nm. First, the mesoscopic films of TiO2 were cast on fluorine-
usually protected by ligands, choosing an appropriate ligand is doped tin oxide (FTO) glass electrode, which was then
the key factor; the ligands will protect the cluster while allowing immersed in the gold cluster solution for 48 h. Then the gold
the exposed metal surface to interact with smaller molecules. cluster modified TiO2 electrode was sandwiched with a Pt-
Tsukuda et al.656 have shown that gold clusters stabilized with deposited FTO counter electrode. Co(bpy)3(PF6)2/Co-
8240 DOI: 10.1021/acs.chemrev.6b00769
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Table 6. Catalytic Performance of Selected Clustersa

cluster average size type of catalysis support type of catalytic reaction ref
Au25(PET)18, Au38(PET)24, Au144(PET)60 1−2 nm homogeneous − styrene oxidation, hydrogenation 655
of aldehydes and ketones
Au@PVP ∼1 nm homogeneous − alcohol oxidation 414−416
Cu@(PAMAM−OH) 1.2 ± 0.3 nm homogeneous − hydrogenation of carbonyl and 677
olefin groups
Au25(PET)18 ∼1 nm homogeneous − hydrogenation of cyclic ketone 678
Au25(PET)18 ∼1 nm homogeneous − hydrogenation of aldehydes and 645
ketones
AuAg@PVP 1.3−2.2 nm homogeneous − alcohol oxidation 679
Au11Cl3(PPh3)8, Au25(PET)18, Au55(PPh3)12Cl6, 0.8−1.7 nm homogeneous − electroreduction of O2 680
Au140(S(CH2)5CH3)53
Au25(SG)18 ∼1 nm homogeneous − electrooxidation of ascorbic acid 681
Au25(PET)18 ∼1 nm homogeneous − electroreduction of CO2 to CO 662
Au@PoPD ∼3 nm homogeneous − aerobic oxidation of alcohols 682
Au@THPC 2.0 ± 0.3 nm homogeneous − aerobic oxidation of alcohols 683
Au@PS 1−2 nm homogeneous − aerobic oxidation of alcohols 684
Au@PAA-1 2.4 ± 0.7 nm homogeneous − aerobic oxidation of alcohols 685
Au@Poly(EOEOVE) <4 nm homogeneous − alcohol oxidation 686
Au@PNIPAM 2.6 ± 1.0 nm homogeneous − aerobic oxidation of alcohols 687
Au@PVP − homogeneous − N-formylation of amines 688
Au@PVP 1.3 nm homogeneous − oxygenation of benzylic ketones 689
Au@PVP 1.3 nm homogeneous − oxidation of organoboron 690
compounds
Au@PVP 1.3 nm homogeneous − intramolecular addition of alcohols 691
to alkenes
Au@PVP 1.3 nm homogeneous − intramolecular addition of 692
toluenesulfonamide
Au@PVP 1.3 nm homogeneous − intramolecular addition reactions 693
of primary amines
Au38(PET)24 1.1 nm heterogeneous CeO2 CO oxidation 694
Aunb 1−6 nm heterogeneous TiO2 CO oxidation 695
Au25(SR)18b ∼1 nm heterogeneous HAP styrene oxidation 696
Aum(SG)n, <2 nm heterogeneous HAP cyclohexane oxidation 672
(m, n) = (10, 10), (18, 14), (25, 18), and (39, 24)b
Au38(PET)24 ∼1.1 nm heterogeneous TiO2, Fe2O3, and oxidation of sulfide to sulfoxide 697
CeO2
Au∼10b ∼0.5 nm heterogeneous FeOOH CO oxidation 698
Au144(PET)60b 1.67 ± 0.2 nm heterogeneous CuO−mSiO2 CO oxidation 699
Au25(PET)18 ∼1 nm heterogeneous TiO2, Fe2O3, and CO oxidation 23
CeO2
Pt1Au24(SC2H4)18 ∼1 nm heterogeneous TiO2 styrene oxidation 199
Pd1Au24(SC2H4)18b ∼1 nm heterogeneous CNT alcohol oxidation 663
Au11@TPPb 0.8 ± 0.3 nm heterogeneous mSiO2 alcohol oxidation 700
Au55(PPh3)12Cl6 ∼1.4 nm heterogeneous SiO2 styrene oxidation 660
Au25(PET)18 ∼1 nm heterogeneous CeO2 homocoupling of aryl iodides 701
Au25(SR)18 ∼1 nm heterogeneous TiO2 photocatalytic degradation of 702
methyl orange
Ag7,8(H2MSA)7,8 <1 nm heterogeneous SiO2, TiO2, reduction of nitrophenol 664
Fe2O3, and
Al2O3
a
It is important to mention here that in many cases, the actual cluster is almost completely inactive. Only after removal of ligands shell, they will be
active for catalysis. Such clusters where the ligand shell is removed are labeled with a. bThe nature of the cluster core may be affected by ligand
desorption.

(bpy)3(PF6)3 was used as an electrolyte in the experiment. The consisting of CdS/ZnS modified TiO2 electrode (Figure 27).706
photocurrent action spectrum shows the maximum incident The maximum power conversion efficiency (η) of MCSC was
photon to photocurrent efficiency (IPCE) of MCSC to be 70% in the range 2.03−2.36%, similar to the value (2−3%) reported
(Figure 27) in the range 400−425 nm, which is relatively higher for QDSC.707,708 The effectiveness of these MCSCs is because
than the IPCE of glutathione protected Au25 cluster (5−15%) of the higher HOMO/LUMO energy gap and stronger
reported by the Tatsuma group.704,705 The high IPCE value in interaction with TiO2, which allows substantial electron
the 400−425 nm region indicates the high efficiency of this injection. The role of Co(II)/Co(III) was to deliver a steady
system to convert the absorbed incident photons into electrical photocurrent. Recently, Abbas et al. have explored the cluster
energy. Its quantum efficiency was closer to the IPCE value size effect on solar cell performance by selecting four differently
(80%) of a comparative quantum dot solar cell (QDSC) sized gold clusters such as Au10−12(SR)10−12, Au15(SR)13,
8241 DOI: 10.1021/acs.chemrev.6b00769
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fast-responding single particle sensors. Composite materials

with graphene, gels, proteins, and oxides are known with
varying properties from antimicrobial to catalytic effects.
Current achievement in the area suggests the expansion of
these materials into biological applications711 and water
purification.712,713
10.1. Graphene Composites
After C60 and nanotubes, graphene is perhaps the most exciting
analogue of carbon, and it has been intensely explored in the
recent past.714−716 Creation of new materials using graphene is
a fascinating area of research, and several nanocomposites have
been made with graphene to incorporate diverse properties in a
single system.513 Chandrasekar and Pradeep54 have illustrated
the possibility of synthesizing a composite of graphene and
silver clusters through covalent linkages (Figure 28a).
Graphene, which contains carboxylic acid groups, was further
functionalized to form thiolated graphene that was used in a
ligand exchange reaction to generate the composite. The
composite was purified by the phase transfer method. The
optical properties of the composite exhibited the features of the
cluster as well as graphene. Interestingly, the cluster
fluorescence was only quenched when a high concentration
Figure 26. (a) Synthetic scheme of Au25/CNT and PdAu24/CNT of the thiolated graphene was used for the exchange process. A
catalyst. (b) Comparative conversion efficiency of two catalysts.
variety of nanocomposites can be generated by varying the
Reprinted from ref 663. Copyright 2012 American Chemical Society.
functional groups, length, and properties of the linker
molecules. Such composites can be used in several applications
Au18(SR)14, and Au25(SR)18, respectively. Among them, such as bioimaging,717 biosensors,718 antibacterial activity,513
Au18(SR)14 shows a conversion efficiency of 3.8%.709,710 This etc. Wang et al.717 have shown the use of a transferrin
highlights the possibility of utilizing noble metal nanoclusters as functionalized gold cluster−graphene oxide nanocomposite for
sensitizers because of their wide range of photoabsorption bioimaging of cancer cells (Figure 28b). In this system,
capacity covering the entire visible window. transferrin acts as a reducing agent as well as a functional ligand
for targeting the transferrin receptor. We believe that several
10. NEW MATERIALS
such new materials can be developed in the future having
Nanomaterials in conjunction with other materials can give implications in diverse fields.
exotic properties. In this context, clusters embedded in soft and
10.2. Other Composites
inorganic materials are a new addition. Attachment of clusters
to nanoparticles has led to enhancement of the luminescence Boron nitride sheets have drawn significant attention because of
and associated properties of metals. Such properties in the their graphene-like 2D layer structure. They also have high
context of mesostructures have enabled the development of temperature stability, high mechanical strength, low dielectric

Figure 27. (a) Schematic view of the working principle of a metal cluster sensitized solar cell. (b) IPCE spectra (external quantum efficiency) of
photoelectrochemical cell using photoanodes composed of (i) TiO2−Aux−SH cluster, (ii) TiO2−CdS/ZnS, and (iii) TiO2. Traces i and iii were
recorded using 0.22 M Co(bpy)3(PF6)2, 0.033 M Co(bpy)3(PF6)3, 0.1 M LiClO4, and 0.5 M 4-tert-butylpyridine in acetonitrile as electrolyte and Pt
deposited on FTO as counter electrode. Trace ii was recorded using 2 M Na2S and 2 M S in H2O as electrolyte and Cu2S-RGO film deposited on
FTO as counter electrode. Reprinted from ref 24. Copyright 2013 American Chemical Society.

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Figure 28. (a) UV/vis spectra of freshly prepared Ag nanoclusters in aqueous phase (brown trace), graphene−GSH (orange trace), and GRN−Ag
nanocluster (violet trace). Inset i shows the photographs of the composite in water (left) and phase transfer to organic medium (right) under visible
and UV light, respectively. Inset ii is the scheme of composite formation. Reprinted from ref 54. Copyright 2012 American Chemical Society. (b)
Schematic of transferrin functionalized gold nanocluster−graphene oxide nanocomposite (i). Corresponding emission spectrum and photographs
under visible and UV lights are given in (ii). Fluorescence imaging of HeLa tumor bearing mice (iv) and normal nude mice (iii). Reprinted from ref
717. Copyright 2013 American Chemical Society.

Figure 29. (a, b) TEM images of Ag44@Te NWs at different magnifications. Ag44(SR)30 aggregates on the NW surface upon exposure to the electron
beam are seen as nodules in (b). (c) Schematic illustration of the aligned NW assembly. Processes involved during the assembly formation are
shown. (d) TEM image of the monolayer assembly formed at the air−water interface in the case of pristine Te NWs. A schematic of the oriented
monolayer of Te NWs is shown in the inset. (e) TEM image of the crossed assembly formed with Ag44@Te NWs for the same NW concentration as
the pristine Te NWs. Schematic illustration of the crossed bilayer structure of the assembly, seen as a woven NW pattern in the TEM image, is
shown in the inset. (f) Expanded view of the marked region in (e) showing uniform inter-NW distances (≈3.4 nm) for both the layers. Reprinted
with permission from ref 721. Copyright 2016 John Wiley & Sons.

constant, and high thermal conductivity. Combining these Such composites can also be useful in drug delivery and
properties of BN sheets with those of gold nanoclusters could diagnosis. George et al.552 made a luminescent chitosan
lead to new composite systems with a potential for different composite of gold cluster encapsulated in cyclodextrin for
applications. Yang et al.719 prepared such composites by specific detection of Cu2+ ion. Mathew et al.554 incorporated 15
dispersing exfoliated BN sheets in poly diallyl-dimethylammo- atom BSA protected silver cluster on a silica coated gold
nium chloride (PDDA) and then decorating the PDDA−BN mesoflower, which was then used as a fluorescence probe for
sheets with orange luminescent gold nanoclusters (GNC). This sensing TNT. Details of these two systems have been discussed
composite was then used to immobilize antibody conjugates previously in section 9.1. Liu et al.720 simultaneously
(Ab2) to fabricate PDDA−BN−GNC−Ab2 bioconjugates used determined ascorbic acid, dopamine, and uric acid via a
as fluorescence probes to detect interleukin-6 (IL-6). The graphene−multiwall carbon nanotube−gold nanocluster com-
PDDA−BN−GNC−Ab2 composite was then used as a biolabel posite modified electrode.
for immunosensing using ITO chips. The limit of detection was In a recent report,721 Som et al. have created Ag44−Te
found to be as low as 0.03 ng/mL. nanowire (NW) composite materials which formed highly
8243 DOI: 10.1021/acs.chemrev.6b00769
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organized crossed bilayer assemblies at the air−water interface

(Figure 29).721
Cluster attachment to the NWs was confirmed by electron
microscopy studies of the Ag44@Te NWs (Figure 29a,b). It is
very difficult to identify individual Ag44(SR)30 clusters (as they
do not produce enough contrast) in standard electron
microscopy on a thick Te NW surface. However, existence of
the cluster can be probed through TEM as high energy electron
beam irradiation creates aggregation (Figure 29b). The cluster
composite shows unusual orthogonal bilayer assembly at the Figure 30. Crystal structure of the left-handed enantiomer of
air−water interface (Figure 29c,e). Note that only Te NWs Au38(PET)24. (a) Top view of the cluster; (b) side view; (c) schematic
show single layer assembly under the same condition (Figure representation highlighting the handedness of the cluster. The inner
29d). This assembly has been directed through hydrogen triangle represents the top three core atoms binding to the long
staples. The arrows represent long staples, and the outer triangle
bonding between the protecting ligand shells of Ag44(MBA)30
represents the core Au atoms binding to the “end” of the staple. This
cluster anchored on NWs. Ag44 cluster layers remain representation is a top view along the C3 axis, and the two triangles are
sandwiched between two of the neighboring NWs at a constant not in one plane. (d) Top view in space-filling representation mode,
distance which is dictated by the core size of the Ag44(SR)30 (e) side view in space-filling representation mode. (f) CD spectra of
cluster (Figure 29f). On the other hand, orientation of the isolated enantiomers 1 (black) and 2 (red) and the racemic
ligands in the space dictates the interlayer geometry. MBA Au38(PET)24 (blue), respectively. Reprinted with permission from
protected Au102 cluster anchored on Te NWs also shows a ref 20. Copyright 2012 Nature Publishing Group.
similar assembly. Such bilayer assembly of the composite
materials can be used for strain sensing.

11. OPTICAL CHIRALITY PET)24744 and Au28(TBBT)20 (TBBT = 4-tert-butylbenzene-

thiolate) 320 by chiral HPLC. For Au102(PMBA)44, the
Chirality has become an intensive research topic for nanoscale enantiomers were enriched during phase transfer with a chiral
materials.722−725 In clusters of the kind discussed here, chirality ammonium salt as phase transfer agent.745 Chirality can also be
could arise because of the following four reasons: (i) ligands induced to an achiral cluster through ligand exchange with
arrangement on the cluster surface, (ii) cis/trans isomerism in chiral ligands.746 Yao et al.729,747 achieved chirality in
the bridged Au−S rings, (iii) inherent chirality of the cluster monolayer protected silver clusters by introducing chiral thiols.
core, and (iv) chiral thiolate ligands.722 Apart from the last one, Dolamic et al. have shown that an intrinsically chiral gold
which is investigated for several nanoparticles, others are cluster, Au38(2-PET)24 (2-PET = 2-phenylethylthiolate), can
important topics to explore and not many reports exist on transfer its handedness to an achiral molecule (2-PET)
them. Strong chiroptical properties of gold nanoclusters were adsorbed on its surface.748 The cluster enantiomers show
observed first by Schaaff et al.227 Since then several examples strong vibrational circular dichroism (VCD) signals in
have been reported.230,350,404,726−730 Optical chirality is vibrations of the achiral adsorbate which could be due to the
typically probed with circular dichroism (CD)230,404,727,729,731 chirality transfer from the cluster to 2-PET.748 The chirality in
and sometimes with vibrational circular dichroism 2-PET arises because of the mirror symmetry breaking, which
(VCD),726,732 along with NMR spectroscopy. Detection of favors one enantiomer of a transiently chiral molecule. Such
the differential absorption of left- and right-circularly polarized chirality transfer can play an important role in enantioselective
light by a chiral sample is the basic principle of CD, whereas chiral catalysis.
VCD is sensitive to the absolute configuration as well as the
conformation of a chiral molecule in solution. Normally, achiral 12. SIMILAR STRUCTURES
molecules or racemic mixtures do not show any VCD activity
Confinement in the subnanoscale occurs in several other
as, without a chiral environment, the two enantiomeric forms of
systems. While similar structure exists in a range of materials
the chiral conformation are equally abundant.722 To explain the
such as zeolites, clathrates, metal organic frameworks (MOFs),
optical activity of these molecules, several models such as chiral
etc., molecular clusters of similar nature exist in a few
footprint model,727,733 intrinsic core chirality,734,735 etc., have
chemically similar systems. Metal hydrides are important
been proposed. Au34− and Au55 have been proposed to have
analogues, hydrides can exist at the center of such metal
inherent chiral cluster cores,174,736−738 but it is very difficult to
clusters. A related category of materials exhibiting molecular
explore with CD as the structural distortion from symmetry is
cluster behavior is semiconductor quantum dots.
very small to be detected. X-ray diffraction and microscopic
techniques739−742 are very helpful in such cases; e.g. chiralities 12.1. Hydride-Rich Silver Clusters
of Au102(SR)4445 and Au40(SR)24743 were seen through XRD. Generally these thiolated clusters are synthesized using a
Au38(2-PET)24 cluster is an example of clusters which show chemical reduction method in which the metal precursors,
ligand arrangement induced chirality. Au38(SR)24731 is a prolate thiol, and NaBH4 are mixed. It is important to see whether
shaped cluster containing a face fused bicosahedral Au23 hydride ions can exist in the final clusters. To the best of our
core.330 This core is further protected by six Au2(SR)3 and knowledge, there is no report in the literature on hydrido−gold
three Au(SR)2 staple motifs. The bare core exists in D3h clusters stabilized by thiol as it is extremely difficult to probe
symmetry, and the staples arrange in a chiral fashion to adopt them with spectroscopy, but a few studies on Au(I)−hydrido
D3 symmetry which leads to chirality in the system because of complexes are known.749,750 In the case of silver clusters, there
their orientation.20 The enantiomers can be separated through are some reports of hydrido compounds stabilized by chalcogen
HPLC and examined by CD spectroscopy as seen in Figure donor ligands. These are believed to be intermediates in the
30.20 Similar enantiomeric separation was reported for Au40(2- formation of noble metal nanoclusters.
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Figure 31. (a) Ag7H core of the cluster disordered in two orientations (50% each). (b) Molecular structure of [Ag7(μ4−H) (Se2P(OiPr)2)6] (30%
thermal ellipsoid) with isopropyl groups omitted for clarity. Reprinted from ref 751. Copyright 2013 American Chemical Society. (c)
Characterization of [Ag18H16(TPP)10]2+ cluster. (i) Positive-mode ESI mass spectra of the cluster. Inset ii shows the corresponding UV/vis spectrum
along with a photograph of the cluster in MeOH. Inset iii shows an expanded view of the molecular peak plotted with the corresponding simulated
spectrum (red trace). Reprinted from ref 752. Copyright 2016 American Chemical Society.

Figure 32. (a) Absorption (black trace), excitation (blue trace), and emission (red trace) spectra of the [Ag62S13(SBut)32](BF4)4 cluster. Inset shows
the corresponding photograph under visible and UV light. (b) Crystal structure of the silver sulfide cluster: (i) centrosymmetric structure of the
cationic part of [Ag62S13(SBut)32](BF4)4, (ii) [Ag14S13] core configuration, and (iii) Ag48(SBut)32 shell structure. The [Ag14S13] core and the tert-
butyl groups have been omitted for clarity, and the artificial large purple sphere shows the inner space occupied by the [Ag14S13] core. Color legend:
orange, Ag (core); green, Ag (shell); purple, S2−; yellow, S (thiolate); gray, C. Reprinted from ref 761. Copyright 2010 American Chemical Society.

Liu et al.751 have shown an example of such intermediate hydride for all these clusters. The numbers of free electrons for
silver clusters, Ag7(H)[E2P(OR)2]6, which can transform to these hydride-rich clusters have been calculated in the same
nanoparticles later. Crystal structures of such hydride clusters way as mentioned in section 1. Hydrides are considered as
have been solved with different ligands (E = S, Se and with electron withdrawing ligands (similar to thiols), and therefore,
different R). The cluster exhibits a tricapped tetrahedral Ag7 the numbers of free electrons for the above-mentioned three
skeleton, which is inscribed within an E12 icosahedron clusters ([Ag18 H16(TPP)10]2+, [Ag25H 22(DPPE)8 ]3+, and
constituted by six dialkyl dichalcogenophosphate ligands in a [Ag26H22(TFPP)13]2+) are 0 (18 − 16 − 2), 0 (25 − 22 −
tetrametallic-tetraconnective (μ2, μ2) bonding mode (Figure 3), and 2 (26 − 22 − 2), respectively (note that phosphines do
31). In general such clusters are synthesized by the reduction of not enter into the free electron count). The third one
the precursor using NaBH4.753,754 The presence of a central completes the electron-shell closing rule which explains its
hydride was probed by 1H, 2H, and 109Ag NMR spectroscopies. stability, whereas for the first two cases stability comes from the
Similar structures have also been found for Cu,755−757 and they geometry. All of these clusters have distinct optical features (an
are used for H2 production using solar energy.758 Very recently, example is given in Figure 31c, for the Ag18 cluster) and the first
Bootharaju et al.752 have synthesized three new hydride-rich two cluster solutions have a unique green color similar to the
silver clusters, namely [Ag18H16(TPP)10]2+, “green gold” compound by Crasto et al.759 The cluster
[Ag25H22(DPPE)8]3+, and [Ag26H22(TFPP)13]2+, using hydrides assignments were done based on the HRESI MS data (Figure
and different phosphines having single or multiple binding sites, 31c) where the molecular peak comes with good isotropic
such as triphenylphosphine (TPP), 1,2-bis- distribution. Discovery of such hydride-rich metal clusters
(diphenylphosphino)ethane [DPPE], and tris(4-fluorophen- shows that smaller ligands can also act as protecting ligands,
yl)-phosphine [TFPP], respectively. NaBH4 was the source of and many clusters can be revisited to see the existence of
8245 DOI: 10.1021/acs.chemrev.6b00769
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Figure 33. (a) MALDI mass spectrum of MBT-protected Pt nanoclusters in negative ion mode, obtained for DMF-protected Pt nanoclusters by
ligand exchange with MBT. Inset shows the extended mass spectrum of Pt5(MBT)7 along with the corresponding calculated spectrum. Reprinted
with permission from ref 775. Copyright 2010 Royal Society of Chemistry. (b) Excitation (dashed line) and emission (solid line) spectra of yellow-
emitting Pt nanoclusters. Inset shows the photograph under UV irradiation (λ = 366 nm). Reprinted from ref 776. Copyright 2012 American
Chemical Society.

hydride in the clusters, as in most of the cases NaBH4 was used [Ag 344 S 124 (SBu t ) 96 ], 765 [Ag 352 S 128 (S t C 5 H 11 ) 96 ], 766 and
as the reducing agent. Buckart et al.760 have shown an [Ag490S188(StC5H11)114].766 Recently Manju et al. have reported
anomalous behavior of hydride in the case of gas phase gold a highly luminescent Ag56Se13S15 cluster which shows Hg2+
clusters where hydride mimics gold. However, one should not detection at 1 ppb level.767
get confused in making the electron count, considering the
electrons of hydride, as chemistry in the solution phase and 13. ATOMICALLY PRECISE Pt AND Pd CLUSTERS
chemistry in the gas phase are completely different. Also, while So far, we have discussed mainly thiolated gold and silver
dihydrogen was the source of hydrogen in the gas phase, clusters. In this section we will briefly describe nanoclusters of
borohydride was the only source of hydride in the solution. other noble metals such as Pd768 and Pt.193 Very few reports
12.2. Silver Sulfide Clusters can be found for these metal nanoclusters. Their reduced
Monolayer protected silver sulfide clusters are another class of stability (compared to gold) in the zero oxidation state makes it
materials which have properties similar to those of the noble difficult to synthesize and characterize them. It is important to
metal nanoclusters. Although very few articles are reported in mention the early work of the Dahl group769−771 on carbonyl
the literature on this specific topic, these systems can give a protected Pd and Pt clusters, but in this section we are focusing
deep insight into the metal sulfide chemistry. These materials largely on thiolated clusters. Apart from Pt and Pd clusters, only
are the smallest versions of quantum dots. They are atomically two reports exist for another noble metal, namely Ir.772,773
precise, while such characterization is usually not possible for 13.1. Platinum Clusters
quantum dots. Li et al.761 deciphered the single crystal structure Synthesis of monodispersed Pt nanoparticles began with the
of an atomically precise silver sulfide nanocluster, report of Kimura and Chen in 2001.774 Kawasaki et al.775
[Ag62S13(SBut)32](BF4)4, which also exhibited luminescence. demonstrated the first surfactant-free solution phase synthesis
The cluster was synthesized by heating three components: of highly stable Pt nanoclusters. High temperature reduction in
AgBF4, H2NNH2, and AgSBut. The thiol acts not only as a DMF was the key factor that led to the generation of this
protecting agent but also as a source of S2− by the cleavage of cluster. The assignment, Pt5(MBT)7, was made from the
the −C−S bond.761 The cluster displayed unique UV/vis MALDI MS data of the ligand exchanged (with 2-mercapto-
features (bands in the UV regions and a low energy band at 543 benzothiazole) cluster which showed an intense peak at m/z
nm) along with a sharp emission at 621 nm (when excited at 2140. The experimental spectrum matched exactly with the
497 and 591 nm) (Figure 32a). The single crystal data corresponding calculated one (Figure 33a). Two other peaks
suggested that the cluster possessed a core/shell geometry. It seen on either side of the main peak were assigned as
can be seen from Figure 32b that the core is made up of 14 Ag+ Pt6(MBT)7 and Pt4(MBT)7, respectively. Le Guével et al.776
ions and 13 sulfur ions. Eight of the 14 Ag+ ions form a cubic synthesized glutathione protected yellow emitting Pt nano-
structure, with the remaining six Ag+ ions positioned at the clusters, which showed emission at 570 nm (Figure 33b).
center of the tetrasilver square faces (Figure 32b,ii). Out of the Tanaka et al. used mercapto acetic acid protected blue emitting
13 sulfur atoms, one is at the center of the core and the platinum nanoclusters for bioimaging of HeLa cells.777 In the
remaining 12 are located on the 12 edges. This core is further experiment, they labeled the cluster with chemokine receptors
surrounded by a Ag48(SBut)32 shell.761 The Ag+ in the shell can in living HeLa cells through a conjugated protein bound
be classified into 36 surface ions and 12 subsurface ions. The antibody. Yuan et al.279 have demonstrated that reversible
thiolates can coordinate to three surface silver atoms or to one phase transfer can lead to blue emitting Pt nanoclusters. They
subsurface and two surface silver atoms. In another work, Li et also showed the effectiveness of this method for other metals
al. 7 6 2 have reported a nest-like structure for the such as Au, Ag, and Cu.279 Chakraborty et al. have synthesized
[Ag33S3(SBut)16(CF3COO)9(NO3)(CH3CN)2](NO3) cluster. atomically precise blue emitting platinum clusters through the
Some of the other known examples of silver sulfide clusters solid state route.193 Mass spectral (both ESI and MALDI MS)
are Ag 5 6 S 1 2 (SBu t ) 2 0 ], 7 6 3 [Ag 7 0 S 2 0 (SPh) 2 8 (dppm) 1 0 ]- characterization yielded an assignment of Pt11(BBS)8, where
(CF3CO2)2,764 [Ag123S35(SBut)50],765 BBS refers to 4-tert-butylbenzyl mercaptan. The cluster was
[Ag262S100(SBut)62(dppp)6],764 [Ag320S130(SBut)60(dppp)12],766 blue emitting with a QY of 3 × 10−3, which is much smaller
8246 DOI: 10.1021/acs.chemrev.6b00769
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Figure 34. (a) Borromean rings diagram of Au25(SMe)18. The core Au atoms are numbered from 1 to 12, and the staple atoms are numbered
clockwise from the end of the staple, from 1 to 5. The lines that join core Au atoms on opposite ends of the same staple are shown by the green lines.
The staple directions are labeled by the six staple locants D1 to D6, marked in red. Inset i shows a 3D visualization of the ring structure of the core
and staples of Au25(SR)18 aspicule, with each (Au8S6) ring consisting of two coplanar staples and the core atoms that are bonded to these staples. See
that there are three distinct, interconnected Au8S6 rings in green (x axis), blue (y axis), and red (z axis). The R group used here is CH3. Inset ii shows
a close-up of the numbering scheme of the core atoms marked on the edge projection of the core icosahedron. Modifications of Au25(SMe)18 with
ligand and metal atom substituents for the following cases: (b) a single bridging ligand (PET) exchange and (c) six bridging ligands and five metal
(Pd) atoms exchanged (which is at present a hypothetical structure). Taken from ref 232. Copyright 2015 American Chemical Society.

than the cluster reported by Tanaka et al.777 Besides the above- many reports of Pd nanoclusters are there today to conclude
mentioned cases, there are also reports of other platinum the presence of such a PdS layer in between the metallic core
nanoclusters.778−784 and thiolate ligands. In 2001 Zamborini et al.797 synthesized
13.2. Palladium Clusters alkanethiolate protected Pd clusters and compared their
For palladium, most of the reports are on nanoparticles, with reactivity, electrochemistry, and properties to those of the
TEM as the main characterization technique.785−793 In many corresponding monolayer protected gold clusters. Their
cases, the Pd nanoparticles were seen to have completely significant difference from Au MPCs drew the interest of
different structures than Au or Ag NPs.794−796 An unusual
sulfidized Pd layer was seen in between metallic core and other groups to work in this area. Negishi et al.798 characterized
thiolated shell. Corthey et al.796 have explained the possible thiolated Pd clusters via mass spectral analysis. Two major
reason for such PdS layer formation in thiolated Pd peaks corresponding to Pd5(SC18H37)10 and Pd10(SC18H37)12
nanoparticles. According to them, initial Pd(0) clusters, formed were seen in the MALDI MS spectrum using anthracene as the
due to the reduction of Pd(II) species, are likely to be matrix. The average cluster core diameter was found to be ∼1
responsible for the S−C bond cleavage which leads to the
nm, consistent with the formula Pdn(SR)m, where m = 0.6n.798
formation of adsorbed sulfide. Once such a PdS layer formed,
the clusters are still active for the adsorption of thiolate From the optical spectrum a band gap of ∼2 eV was observed
moieties but cannot decompose further, which results in the which showed the emergence of nonmetallic properties as a
formation of Pd@PdS@SR type of nanoparticles. However, not result of size reduction.798
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14. NAMING AND STRUCTURAL UNDERSTANDING

The discussion presented suggests that cluster systems behave
as (a) molecules with (b) constituent units such as ligands and
cores retaining their limited individualities while (c) the
integrated entity behaves as an independent molecular unit in
properties and functions. The most important single aspect that
comes out of these studies is that clusters of this type are
molecules-in-molecules and each of the constituents is essential
for the integrity of the whole. They may be regarded as
molecules protected with molecules. A detailed analysis of
clusters was made by Natarajan et al. to suggest the compound
name aspicule for this class of systems which is derived by
combining the Greek root word aspis meaning “shield” with
cule of “molecule”, meaning “shielded molecule”, reflecting their
chemical, physical, and material character.232 This name is
suggested with the realization that, without a proper name, the
variety and complexity of chemistry being evolved cannot be
captured. Imagine, for example, ligand exchange changing the Figure 35. Plot of number of ligands with respect to the number of
composition of the cluster. With multiple ligands being metal atoms for gold and silver clusters reported so far. Inset shows the
same plot for clusters with crystal structures.
exchanged at specific locations, there is a need to indicate the
binding sites. Some of these clusters may be isomeric in terms
of their positions. In order to name different isomeric structures various ligand and metal positions are possible, and they can be
uniquely, a systematic way of drawing these structures is presented and labeled. A recent report of Au25 dimer and its
needed. A set of rules for naming the clusters is essential. Such associated isomers480 can easily be explained with this model
naming systems have been introduced already for fullerenes and structure.
boranes.
Aspicule nomenclature has been proposed for the three most 15. FUTURE PROSPECTS
common gold clusters, Au 25 (SR) 18 , Au 38 (SR) 24 , and The evolving interface of nanoparticles and clusters is being
Au144(SR)60, which may be extended further for other clusters. enriched by a large variety of molecular species with chemical
The structure of an aspicule may be represented as three diversity. Looking into the future, several avenues of
concentric shells of atoms: (i) the protective shell of ligand R unprecedented growth are evident. In the following, we
groups, (ii) an intermediate mantle, and (iii) the inner metal attempt to capture some of these exciting areas.
core. The most common geometry for the inner core is 15.1. New Synthetic Methodologies
icosahedral due to its high stability. They have simplified the Even though a wide series of gold clusters with different
structural representation in the form of a diagram (Figure 34a) nuclearities have been synthesized so far (Figure 35), reports
with unique positional labels (locants) for (i) the core atoms, on silver clusters are limited and the list is just a handful for
(ii) the staples, (iii) the ligands, and (iv) the staple metal atoms. other noble metals. Significant improvement in synthetic
Among the several possible structural representations and methodology is needed in order to create variety in noble
labeling schemes for Au25, a simple topological representation metal cluster science. It can also be extended to other metals
was found based on a projection of the three-ring structure of such as Cu211,758,799−801 and Fe.802 Choice of ligands can solve
Au25(SR)18, with all of the essential atoms and the octahedral the problem in many cases as can be seen in the recent reports.
symmetry as depicted in Figure 35a. Tuning the thiol and phosphine ratios, use of carboxy and other
For developing the aspicule nomenclature these four points oxy ligands for metals like Cu and Pd, use of hydride as ligand,
were taken care of: (i) symmetry, (ii) universality and ability to etc., are important to consider.
describe the structure and/or modifications of any aspicule, (iii)
15.2. Ligand Induced Properties
resemblance to IUPAC nomenclature, and (iv) simplicity,
enough to use and remember, even for such complex structures. The metallic cores and the ligands, in part, add specific
The name for Au25(SMe)18 according to the “aspicule properties to the cluster system. Several of these properties are
nomenclature” is 18(methylthiolato)-auro-25 aspicule(1−) or complementary, although integrated phenomena based on
(SMe)18-auro-25 aspicule(1−), in its condensed form. individual properties have not been explored adequately. The
Au25(SMe)17(PET)1, based on the locants of Figure 34b, only phenomenon explored to some extent is FRET, which has
which has the PET ligand exchanged at the bridging position 3 been demonstrated in a few cases, in both ligand and protein
on the D3 staple, is (D3-3)-(2-phenylethanethiolato),17- protected clusters. Moving beyond, integration of other
(methylthiolato)-auro-25 aspicule(1−) or, in its condensed properties of the ligand and the core, enhancing electrical
form, (D3-3)-(PET)1,(SMe)17-auro-25 aspicule(1−). Here D3- conductivity, magnetism, optical absorption, thermal conduc-
3 corresponds to the ligand exchanging position. Similarly, an tivity, and catalysis may be explored.
alloy cluster such as Au20Pd5(SMe)12(PET)6 can have its 15.3. Alloys
aspicule name (Figure 34c) as ([D1−D6]-3)-hexa(2- While early science of the complexity of the cluster core in
phenylethanethiolato),dodeca(methylthiolato)-(i,5,6,D3-2,D4- terms of alloying is available, integration of cluster nuclei
4)-pentapalladoauro-25 aspicule(1−) or, in its shorter form, producing more complex multicluster systems is yet to evolve.
([D1−D6]-3)-(PET)6,(SMe)12-(i,5,6,D3-2,D4-4)-pentapalla- One such possibility is cluster dimers and polymers which
doauro-25 aspicule(1−). As can be seen, a variety of isomers for constitute new forms of architectures with unprecedented
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diversity. Such cluster building blocks may present new properties. A comparison of the clusters reported so far and
paradigms in materials science. available crystal structures are presented in Figure 35. Gold and
15.4. Hydride-Rich Clusters silver follow a similar trend, with a few exceptions. It is clear
that there is ample room to discover new structures and the
Recently, isolation of several hydride-rich metal nanoclusters associated properties. One aspect requiring systematic inves-
has shown that smaller ligands like H− can also serve as tigation is the ease of forming crystals of the same core with
protecting agents. In all of these cases, H− comes from the very
chemically similar ligands. Multiple properties of ligands can be
common reducing agent NaBH4, which suggests a new
considered. Chemically constrained ligands such as calixar-
direction of revisiting many of the clusters to check the
enes805−807 have been considered with multiple thiols.
existence of hydride in them. Such clusters may be possible
Nonplanar thiols, dithiols, and such other systems will be of
with other metals, too. It will be interesting to have hydride-rich
use in this context. New crystallization strategies such as
clusters as a potential candidate for hydrogen storage, although
this appears to be an expensive and “heavy” proposition right electrocrystallization reported recently808 may be extendable to
now. Note that mass storage efficiency here is much lower than other clusters.
in materials such as magnesium hydrides. Cluster crystals as materials have not been examined. While
crystal structures have been looked at, studies have not gone
15.5. Cluster Composites beyond to determine the properties of crystals such as electrical
The interface of inorganics and organics through clusters is conductivity, optical properties, temperature, pressure effects,
another fascinating area. While there are many bioconjugates, etc. A rich area of cluster materials is yet to be explored.
the inherent advantages of clusters with luminescence, catalysis, 15.9. Intercluster Reactions
and functionality, along with reduced sizes, provide new
capabilities for chemical interactions, and the composites can Spontaneous reactions involving metal and ligand exchange and
access much smaller volumes than hitherto accessible by the new examples of isomorphous transformations310 between
nanoparticles and can report on the events in the vicinity with clusters suggest that many new examples of this science are
better spatial accuracy. We hope that such new reports will possible. In this process, it may be possible to create completely
change our understanding of biosystems significantly. In the new clusters. Transformation of clusters from one to the other
case of inorganics, cluster conjugates with graphene and presents new examples of chemistry at the nanometer length
graphene analogues will be a new direction to pursue. Noble scale. It is likely that these reactions produce new examples of
metal clusters can be conjugated with 2D chalcogenides and nanochemistry.
other quantum structures, using molecular linkers. These 15.10. Cluster Assembled Solids
conjugate systems are likely to be novel ways of imparting
properties to 2D sheets. The materials science of such Ligand protected clusters can be brought to the gas phase from
conjugates will be a new direction forward. Some early solution, and they can be flown through in a gaseous stream.
directions in this context are available.54 This suggests that protecting ligands can be removed, at least in
some cases by thermal or photochemical processes. The
15.6. Computational Approaches
resulting naked clusters could be new reagents as they are
The complex architecture being evolved will require new atomically precise and, in most cases, they will have only one
computational approaches. Early signs of such studies in type of cluster in comparison to many nuclearities that are
cluster−virus interaction are seen in the recent past.803 Precise formed in thermal or other evaporation processes. This naked
understanding at still larger length scale may be feasible. Such cluster based synthesis of advanced materials would make the
studies are expected to point to newer interfaces in cluster synthesis of cluster assembled porous solids possible. As
science. Computations are essential to understand the events in clusters of this kind can be controlled by appropriate charges,
clusters such as the early stages of intercluster reactions, which their deposition can be controlled with electrical or magnetic
are impossible to capture today with the current level of means, allowing patterning. These cluster assembled films may
instrumentation. be useful in creating photonic materials.
15.7. Stabilizing Cluster Luminescence 15.11. Clusters as New Molecules
An important aspect of clusters is their luminescence. However, The science of clusters is becoming analogous to that of
clusters have reduced stability. As a result, there is a need to molecules. Intercluster chemistry has shown several examples,
protect them with appropriate shells with suitable functionality and they suggest that the science of clusters is similar to that of
which allows their penetration into biological and other simple molecules. Clusters with their cores and ligands act as
environments such as polymers, ceramics, etc. A possibility is single entities in these transformations. This new category of
silica protection, which has been examined some time ago.804 chemistry is distinctly different from that of the ligands and the
However, such studies have not been continued. Properties get
cores which have been probed in more detail. Expansion of the
enhanced in confined environments, and this needs to be
area involving new clusters and reaction conditions will open
exploited.
up new areas of science. Ultimately these explorations could
15.8. Crystallization lead to new rules of cluster chemistry analogous to molecular
Molecules of the kind described here have a distinct well- science.
defined core with a precise number of ligands. There are plenty Applications of clusters in terms of sensors, solar cells, and
of clusters in terms of both gold and silver which have been bioimaging have appeared. However, potentially useful
reported recently. Among them, only a few have crystal technologies which could impact industry have not come yet.
structures. Therefore, it is important to develop new strategies These may happen, however, by combining properties of
to obtain crystals of most of the clusters. This is necessary for a clusters with other novel materials such as 2D sheets,
detailed understanding of their structure, bonding, and nanoparticles, and quantum dots.
8249 DOI: 10.1021/acs.chemrev.6b00769
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In closing, it is clear that exploration of the science of clusters research and a postdoctoral fellowship. I.C. thanks Sathi Roy
is expanding chemistry, materials science, and nanoscale for her help in formatting the references and suggestions.
phenomena. The properties of these systems will take their
applications to biology, sensors, catalysis, and several areas of ABBREVIATIONS
materials technology. Their emerging phenomena require new
experimental and theoretical tools for detailed understanding. AAS atomic absorption spectroscopy
New synthetic chemistry is needed to discover unknown cluster AFM atomic force microscopy
systems. On the whole, a bright future is visible; some of the Apt-thrombin 27-Nt DNA aptamer
excitements on the horizon are likely to happen in the areas BSA bovine serum albumin
listed above, although we are aware that predictions are likely to CD circular dichroism spectroscopy
reflect personal preferences. Con A concanavalin A
COSY correlation spectroscopy
ASSOCIATED CONTENT CV cyclic voltammetry
DFT density functional theory
*
S Supporting Information DLS dynamic light scattering
The Supporting Information is available free of charge on the DNA-apt DNA aptamer-templated
ACS Publications website at DOI: 10.1021/acs.chem- DPV differential pulse voltammetry
rev.6b00769. DSC differential scanning calorimetry
Table presenting summary of monolayer protected Au EIND-SH 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacene-4-thio
ESI MS electrospray ionization mass spectrometry
and Ag clusters, synthesized so far (PDF) ET energy transfer
EXAFS extended X-ray absorption fine structure
AUTHOR INFORMATION FTIR Fourier transform infrared spectroscopy
Corresponding Author GST glutathione S-transferase
HAADF high angle annular dark field
*E-mail: [email protected]. hIgG human immunoglobulin G
ORCID HPLC high pressure liquid chromatography
Indranath Chakraborty: 0000-0003-4195-9384 MALDI MS matrix assisted laser desorption ionization mass
Thalappil Pradeep: 0000-0003-3174-534X spectrometer
MUA 11-mercaptoundecanoic acid
Present Address NMR nuclear magnetic resonance spectroscopy
†
I.C.: Department of Physics, Philipps University of Marburg, OSWV Osteryoung square wave voltammogram
Marburg 35037, Germany. PAGE polyacrylamide gel electrophoresis
Notes PAMAM poly(amido) amine
PDGF AA platelet-derived growth factor AA
The authors declare no competing financial interest. PDOS projected densities of states
Biographies PET 2-phenylethanethiol
PL photoluminescence spectroscopy
Indranath Chakraborty earned a Ph.D. in physical chemistry from the SAXRD small angle X-ray diffraction
Indian Institute of Technology, Madras. He was an IIT Madras SAXS small angle X-ray scattering
Institute Postdoctoral Fellow. Later, he was a postdoctoral research SEC size exclusion chromatography
associate at the University of Illinois at Urbana−Champaign, IL, USA. SEM scanning electron microscopy
Currently, he is an Alexander von Humboldt Postdoctoral Research STM scanning tunneling microscopy
Fellow at Philipps University of Marburg, Germany. His Ph.D. work TDDFT time dependent density-functional theory
has been on the formation, functionalization, and applications of TEM transmission electron microscopy
atomically precise silver clusters. He has authored 28 scientific papers Tg thyroglobulin
in journals and is an inventor in four patent applications. He is a TGA thermogravimetric analysis
recipient of the J. C. Bose Patent Award and the Malhotra Weikfield TOA tetraoctylammonium bromide
Foundation Nanoscience Fellowship Award. UV/vis ultraviolet−visible spectroscopy
Thalappil Pradeep is an institute professor at the Indian Institute of XANES X-ray near-edge absorption
Technology Madras, Chennai, India. He is also the Deepak Parekh XRD X-ray diffraction
Institute Chair Professor and professor of chemistry. Besides the work
on nanomaterials, he is involved in the development of affordable REFERENCES
technologies for drinking water purification. His other interests are in
(1) Murray, R. W. Nanoelectrochemistry: Metal Nanoparticles,
ice chemistry, mass spectrometry, instrumentation, and business Nanoelectrodes, and Nanopores. Chem. Rev. 2008, 108, 2688−720.
incubation. He is a fellow of all the science and engineering academies (2) Hühn, J.; Carrillo-Carrion, C.; Soliman, M. G.; Pfeiffer, C.;
of India and is also a Fellow of the Royal Society of Chemistry. For Valdeperez, D.; Masood, A.; Chakraborty, I.; Zhu, L.; Gallego, M.;
more information, please see http://www.dstuns.iitm.ac.in/pradeep- Yue, Z.; et al. Selected Standard Protocols for the Synthesis, Phase
research-group.php. Transfer, and Characterization of Inorganic Colloidal Nanoparticles.
Chem. Mater. 2017, 29, 399−461.
ACKNOWLEDGMENTS (3) Daniel, M. C.; Astruc, D. Gold Nanoparticles: Assembly,
Supramolecular Chemistry, Quantum-size-related Properties, and
Authors acknowledge funding from the Department of Science Applications Toward Biology, Catalysis, and Nanotechnology. Chem.
and Technology, Government of India. I.C. thanks IITM for Rev. 2004, 104, 293−346.

8250 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(4) Schmid, G. Large Clusters and Colloids. Metals in the Embryonic (25) Weissker, H. C.; Escobar, H. B.; Thanthirige, V. D.; Kwak, K.;
State. Chem. Rev. 1992, 92, 1709−1727. Lee, D.; Ramakrishna, G.; Whetten, R. L.; López-Lozano, X.
(5) Aikens, C. M. Electronic Structure of Ligand-Passivated Gold and Information on Quantum States Pervades the Visible Spectrum of
Silver Nanoclusters. J. Phys. Chem. Lett. 2011, 2, 99−104. the Ubiquitous Au144(SR)60 Gold Nanocluster. Nat. Commun. 2014, 5,
(6) Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Atomically Precise Colloidal 3785.
Metal Nanoclusters and Nanoparticles: Fundamentals and Oppor- (26) Bootharaju, M. S.; Joshi, C. P.; Parida, M. R.; Mohammed, O. F.;
tunities. Chem. Rev. 2016, 116, 10346−10413. Bakr, O. M. Templated Atom-Precise Galvanic Synthesis and Structure
(7) Fernando, A.; Weerawardene, K. L. D. M.; Karimova, N. V.; Elucidation of a [Ag24Au(SR)18]− Nanocluster. Angew. Chem. 2016,
Aikens, C. M. Quantum Mechanical Studies of Large Metal, Metal 128, 934−938.
Oxide, and Metal Chalcogenide Nanoparticles and Clusters. Chem. (27) Dass, A. Mass Spectrometric Identification of Au68(SR)34
Rev. 2015, 115, 6112−6216. Molecular Gold Nanoclusters with 34-Electron Shell Closing. J. Am.
(8) Castleman, A. W.; Khanna, S. N. Clusters, Superatoms, and Chem. Soc. 2009, 131, 11666−11667.
Building Blocks of New Materials. J. Phys. Chem. C 2009, 113, 2664− (28) Guo, J.; Kumar, S.; Bolan, M.; Desireddy, A.; Bigioni, T. P.;
2675. Griffith, W. P. Mass Spectrometric Identification of Silver Nano-
(9) Reveles, J. U.; Khanna, S. N.; Roach, P. J.; Castleman, A. W., Jr. particles: The Case of Ag32(SG)19. Anal. Chem. 2012, 84, 5304−5308.
Multiple Valence Superatoms. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, (29) Harkness, K. M.; Cliffel, D. E.; McLean, J. A. Characterization of
18405−18410. Thiolate-Protected Gold Nanoparticles by Mass Spectrometry. Analyst
(10) Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.; 2010, 135, 868−874.
Calero, G.; Ackerson, C. J.; Whetten, R. L.; Gronbeck, H.; Hakkinen, (30) Harkness, K. M.; Tang, Y.; Dass, A.; Pan, J.; Kothalawala, N.;
H. A Unified View of Ligand-Protected Gold Clusters as Superatom Reddy, V. J.; Cliffel, D. E.; Demeler, B.; Stellacci, F.; Bakr, O. M.;
Complexes. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 9157−9162. McLean, J. A. Ag44(SR)304‑: a Silver-Thiolate Superatom Complex.
(11) Chakraborty, I.; Udayabhaskararao, T.; Pradeep, T. High Nanoscale 2012, 4, 4269−4274.
Temperature Nucleation and Growth of Glutathione Protected ∼ Ag75 (31) Kumara, C.; Dass, A. AuAg Alloy Nanomolecules with 38 Metal
Clusters. Chem. Commun. 2012, 48, 6788−6790. Atoms. Nanoscale 2012, 4, 4084−4086.
(12) Niihori, Y.; Matsuzaki, M.; Pradeep, T.; Negishi, Y. Separation (32) Mathew, A.; Sajanlal, P. R.; Pradeep, T. A Fifteen Atom Silver
of Precise Compositions of Noble Metal Clusters Protected with Cluster Confined in Bovine Serum Albumin. J. Mater. Chem. 2011, 21,
Mixed Ligands. J. Am. Chem. Soc. 2013, 135, 4946−4949. 11205−11212.
(13) Kumar, S.; Bolan, M. D.; Bigioni, T. P. Glutathione-Stabilized (33) Qian, H.; Zhu, Y.; Jin, R. Atomically Precise Gold Nanocrystal
Magic-Number Silver Cluster Compounds. J. Am. Chem. Soc. 2010, Molecules with Surface Plasmon Resonance. Proc. Natl. Acad. Sci. U. S.
132, 13141−13143. A. 2012, 109, 696−700.
(14) Udaya Bhaskara Rao, T.; Pradeep, T. Luminescent Ag7 and Ag8 (34) Tsunoyama, R.; Tsunoyama, H.; Pannopard, P.; Limtrakul, J.;
Clusters by Interfacial Synthesis. Angew. Chem., Int. Ed. 2010, 49, Tsukuda, T. MALDI Mass Analysis of 11 kDa Gold Clusters Protected
3925−3929. by Octadecanethiolate Ligands. J. Phys. Chem. C 2010, 114, 16004−
(15) Heaven, M.; Dass, A.; White, P.; Holt, K.; Murray, R. Crystal 16009.
Structure of the Gold Nanoparticle [N(C8H17)4]- (35) Udayabhaskararao, T.; Bootharaju, M. S.; Pradeep, T. Thiolate-
[Au25(SCH2CH2Ph)18]. J. Am. Chem. Soc. 2008, 130, 3754−3755. Protected Ag32 Clusters: Mass Spectral Studies of Composition and
(16) Chakraborty, I.; Govindarajan, A.; Erusappan, J.; Ghosh, A.; Insights into the Ag-Thiolate Structure from NMR. Nanoscale 2013, 5,
Pradeep, T.; Yoon, B.; Whetten, R. L.; Landman, U. The Superstable 9404−9411.
25 kDa Monolayer Protected Silver Nanoparticle: Measurements and (36) Chakraborty, I.; Kurashige, W.; Kanehira, K.; Gell, L.; Häkkinen,
Interpretation as an Icosahedral Ag152(SCH2CH2Ph)60 Cluster. Nano H.; Negishi, Y.; Pradeep, T. Ag44(SeR)30: A Hollow Cage Silver
Lett. 2012, 12, 5861−5866. Cluster with Selenolate Protection. J. Phys. Chem. Lett. 2013, 4, 3351−
(17) Udayabhaskararao, T.; Sun, Y.; Goswami, N.; Pal, S. K.; 3355.
Balasubramanian, K.; Pradeep, T. Ag7Au6: A 13-Atom Alloy Quantum (37) Rao, T. U. B.; Nataraju, B.; Pradeep, T. Ag9 Quantum Cluster
Cluster. Angew. Chem., Int. Ed. 2012, 51, 2155−2159. through a Solid-State Route. J. Am. Chem. Soc. 2010, 132, 16304−
(18) Nishigaki, J.-i.; Tsunoyama, R.; Tsunoyama, H.; Ichikuni, N.; 16307.
Yamazoe, S.; Negishi, Y.; Ito, M.; Matsuo, T.; Tamao, K.; Tsukuda, T. (38) Qian, H.; Zhu, M.; Wu, Z.; Jin, R. Quantum Sized Gold
A New Binding Motif of Sterically Demanding Thiolates on a Gold Nanoclusters with Atomic Precision. Acc. Chem. Res. 2012, 45, 1470−
Cluster. J. Am. Chem. Soc. 2012, 134, 14295−14297. 1479.
(19) Yao, C.; Lin, Y.-j.; Yuan, J.; Liao, L.; Zhu, M.; Weng, L.-h.; Yang, (39) Yang, H.; Lei, J.; Wu, B.; Wang, Y.; Zhou, M.; Xia, A.; Zheng, L.;
J.; Wu, Z. Mono-cadmium vs Mono-mercury Doping of Au25 Zheng, N. Crystal Structure of a Luminescent Thiolated Ag
Nanoclusters. J. Am. Chem. Soc. 2015, 137, 15350−15353. Nanocluster with an Octahedral Ag64+ core. Chem. Commun. 2013,
(20) Dolamic, I.; Knoppe, S.; Dass, A.; Bü r gi, T. First 49, 300−302.
Enantioseparation and Circular Dichroism Spectra of Au38 Clusters (40) Yang, H.; Wang, Y.; Zheng, N. Stabilizing Subnanometer Ag(0)
Protected by Achiral Ligands. Nat. Commun. 2012, 3, 798. Nanoclusters by Thiolate and Diphosphine Ligands and their Crystal
(21) Chakraborty, I.; Udayabhaskararao, T.; Deepesh, G. K.; Pradeep, Structures. Nanoscale 2013, 5, 2674−2677.
T. Sunlight Mediated Synthesis and Antibacterial Properties of (41) Zhu, M.; Aikens, C. M.; Hollander, F. J.; Schatz, G. C.; Jin, R.
Monolayer Protected Silver Clusters. J. Mater. Chem. B 2013, 1, Correlating the Crystal Structure of A Thiol-Protected Au25 Cluster
4059−4064. and Optical Properties. J. Am. Chem. Soc. 2008, 130, 5883−5885.
(22) Muhammed, M. A. H.; Verma, P. K.; Pal, S. K.; Kumar, R. C. A.; (42) Das, A.; Li, T.; Nobusada, K.; Zeng, Q.; Rosi, N. L.; Jin, R. Total
Paul, S.; Omkumar, R. V.; Pradeep, T. Bright, NIR-Emitting Au23 from Structure and Optical Properties of a Phosphine/Thiolate-Protected
Au25: Characterization and Applications Including Biolabeling. Chem. - Au24 Nanocluster. J. Am. Chem. Soc. 2012, 134, 20286−20289.
Eur. J. 2009, 15, 10110−10120. (43) Zeng, C.; Qian, H.; Li, T.; Li, G.; Rosi, N. L.; Yoon, B.; Barnett,
(23) Nie, X.; Qian, H.; Ge, Q.; Xu, H.; Jin, R. CO Oxidation R. N.; Whetten, R. L.; Landman, U.; Jin, R. Total Structure and
Catalyzed by Oxide-Supported Au25(SR)18 Nanoclusters and Identi- Electronic Properties of the Gold Nanocrystal Au36(SR)24. Angew.
fication of Perimeter Sites as Active Centers. ACS Nano 2012, 6, Chem., Int. Ed. 2012, 51, 13114−13118.
6014−6022. (44) Desireddy, A.; Conn, B. E.; Guo, J.; Yoon, B.; Barnett, R. N.;
(24) Chen, Y.-S.; Choi, H.; Kamat, P. V. Metal-Cluster-Sensitized Monahan, B. M.; Kirschbaum, K.; Griffith, W. P.; Whetten, R. L.;
Solar Cells. A New Class of Thiolated Gold Sensitizers Delivering Landman, U.; Bigioni, T. P. Ultrastable Silver Nanoparticles. Nature
Efficiency Greater Than 2%. J. Am. Chem. Soc. 2013, 135, 8822−8825. 2013, 501, 399−402.

8251 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(45) Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; (65) Huang, X.; Jain, P. K.; El-Sayed, I. H.; El-Sayed, M. A. Gold
Kornberg, R. D. Structure of a Thiol Monolayer-Protected Gold Nanoparticles: Interesting Optical Properties and Recent Applications
Nanoparticle at 1.1 Å Resolution. Science 2007, 318, 430−433. in Cancer Diagnostics and Therapy. Nanomedicine 2007, 2, 681−93.
(46) Joshi, C. P.; Bootharaju, M. S.; Alhilaly, M. J.; Bakr, O. M. (66) Huang, X.; Jain, P. K.; El-Sayed, I. H.; El-Sayed, M. A. Plasmonic
[Ag25(SR)18]−: The “Golden” Silver Nanoparticle. J. Am. Chem. Soc. Photothermal Therapy (PPTT) Using Gold Nanoparticles. Lasers
2015, 137, 11578−11581. Med. Sci. 2008, 23, 217−28.
(47) Shichibu, Y.; Negishi, Y.; Watanabe, T.; Chaki, N. K.; (67) Jain, P. K.; Huang, X.; El-Sayed, I. H.; El-Sayed, M. A. Noble
Kawaguchi, H.; Tsukuda, T. Biicosahedral Gold Clusters Metals on the Nanoscale: Optical and Photothermal Properties and
[Au25(PPh3)10(SCnH2n+1)5Cl2]2+ (n = 2−18): A Stepping Stone to Some Applications in Imaging, Sensing, Biology, and Medicine. Acc.
Cluster-Assembled Materials. J. Phys. Chem. C 2007, 111, 7845−7847. Chem. Res. 2008, 41, 1578−1586.
(48) Udayabhaskararao, T.; Pradeep, T. New Protocols for the (68) Jana, N. R. Gram-scale Synthesis of Soluble, Near-Monodisperse
Synthesis of Stable Ag and Au Nanocluster Molecules. J. Phys. Chem. Gold Nanorods and Other Anisotropic Nanoparticles. Small 2005, 1,
Lett. 2013, 4, 1553−1564. 875−882.
(49) Yuan, X.; Luo, Z.; Yu, Y.; Yao, Q.; Xie, J. Luminescent Noble (69) Khlebtsov, N. G.; Dykman, L. A. Optical Properties and
Metal Nanoclusters as an Emerging Optical Probe for Sensor Biomedical Applications of Plasmonic Nanoparticles. J. Quant.
Development. Chem. - Asian J. 2013, 8, 858−871. Spectrosc. Radiat. Transfer 2010, 111, 1−35.
(50) Goswami, N.; Zheng, K.; Xie, J. Bio-NCs - the Marriage of (70) Lin, H.-Y.; Huang, P.-J.; Huang, C.-H.; Wang, Y.-C.; Wang, C.-
Ultrasmall Metal Nanoclusters with Biomolecules. Nanoscale 2014, 6, R. C. In Synthesis and Optical Properties of Noble Metal Nanoparticles for
13328−13347. Biodetection; Pan Stanford Publishing Pte. Ltd.: 2012; pp 1−10.
(51) Mathew, A.; Pradeep, T. Noble Metal Clusters: Applications in (71) Liz-Marzan, L. M. Tailoring Surface Plasmons through the
Energy, Environment, and Biology. Part. Part. Sys. Charact. 2014, 31, Morphology and Assembly of Metal Nanoparticles. Langmuir 2006,
1017−1053. 22, 32−41.
(52) Yang, X.; Wang, E. K. Synthesis and Applications of Silver (72) Nehl, C. L.; Hafner, J. H. Shape-Dependent Plasmon
Nanoclusters Protected by Polymers, Protein, Peptide and Short Resonances of Gold Nanoparticles. J. Mater. Chem. 2008, 18, 2415−
Molecules. RSC Smart Mater. 2014, 7, 100−130. 2419.
(53) Fang, J.; Zhang, B.; Yao, Q.; Yang, Y.; Xie, J.; Yan, N. Recent (73) Long, N. V.; Yang, Y.; Teranishi, T.; Thi, C. M.; Cao, Y.;
Advances in the Synthesis and Catalytic Applications of Ligand- Nogami, M. Biomedical Applications of Advanced Multifunctional
Protected, Atomically Precise Metal Nanoclusters. Coord. Chem. Rev. Magnetic Nanoparticles. J. Nanosci. Nanotechnol. 2015, 15, 10091−
2016, 322, 1−29. 10107.
(54) Chandrasekar, A.; Pradeep, T. Luminescent Silver Clusters with (74) Sarina, S.; Waclawik, E. R.; Zhu, H. Photocatalysis on Supported
Covalent Functionalization of Graphene. J. Phys. Chem. C 2012, 116, Gold and Silver Nanoparticles under Ultraviolet and Visible Light
Irradiation. Green Chem. 2013, 15, 1814−1833.
14057−14061.
(75) Shahbazali, E.; Hessel, V.; Noel, T.; Wang, Q. Metallic
(55) Xavier, P. L.; Chaudhari, K.; Baksi, A.; Pradeep, T. Protein-
Nanoparticles Made in Flow and their Catalytic Applications in
Protected Luminescent Noble Metal Quantum Clusters: an Emerging
Organic Synthesis. Nanotechnol. Rev. 2014, 3, 65−86.
Trend in Atomic Cluster Nanoscience. Nano Rev. 2012, 3, 14767−
(76) Wu, L.; Reinhard, B. M. Probing Subdiffraction Limit
14782.
Separations with Plasmon Coupling Microscopy: Concepts and
(56) Sankar, M. U.; Aigal, S.; Maliyekkal, S. M.; Chaudhary, A.;
Applications. Chem. Soc. Rev. 2014, 43, 3884−3897.
Anshup; Kumar, A. A.; Chaudhari, K.; Pradeep, T. Biopolymer- (77) Zhou, X.; Liu, G.; Yu, J.; Fan, W. Surface Plasmon Resonance-
Reinforced Synthetic Granular Nanocomposites for Affordable Point- Mediated Photocatalysis by Noble Metal-Based Composites under
of-use Water Purification. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, Visible Light. J. Mater. Chem. 2012, 22, 21337−21354.
8459−8464. (78) Chiu-Lam, A.; Rinaldi, C. Nanoscale Thermal Phenomena in
(57) Aikens, C. M. Modelling Small Gold and Silver Nanoparticles the Vicinity of Magnetic Nanoparticles in Alternating Magnetic Fields.
with Electronic Structure Methods. Mol. Simul. 2012, 38, 607−614. Adv. Funct. Mater. 2016, 26, 3933−3941.
(58) Arvizo, R. R.; Bhattacharyya, S.; Kudgus, R. A.; Giri, K.; (79) Gao, Y.; Lim, J.; Teoh, S.-H.; Xu, C. Emerging Translational
Bhattacharya, R.; Mukherjee, P. Intrinsic Therapeutic Applications of Research on Magnetic Nanoparticles for Regenerative Medicine.
Noble Metal Nanoparticles: Past, Present and Future. Chem. Soc. Rev. Chem. Soc. Rev. 2015, 44, 6306−6329.
2012, 41, 2943−2970. (80) Kaewsaneha, C.; Tangboriboonrat, P.; Polpanich, D.; Elaissari,
(59) Azcarate, J. C.; Corthey, G.; Pensa, E.; Vericat, C.; Fonticelli, M. A. Multifunctional Fluorescent-Magnetic Polymeric Colloidal Par-
H.; Salvarezza, R. C.; Carro, P. Understanding the Surface Chemistry ticles: Preparations and Bioanalytical Applications. ACS Appl. Mater.
of Thiolate-Protected Metallic Nanoparticles. J. Phys. Chem. Lett. 2013, Interfaces 2015, 7, 23373−23386.
4, 3127−3138. (81) Lee, N.; Yoo, D.; Ling, D.; Cho, M. H.; Hyeon, T.; Cheon, J.
(60) Bhattacharya, R.; Mukherjee, P. Biological Properties of Iron Oxide Based Nanoparticles for Multimodal Imaging and
″Naked″ Metal Nanoparticles. Adv. Drug Delivery Rev. 2008, 60, Magnetoresponsive Therapy. Chem. Rev. 2015, 115, 10637−10689.
1289−1306. (82) McNamara, K.; Tofail, S. A. M. Nanosystems: the Use of
(61) Chiu, T.-C.; Hu, C.-C. In Biodetection Based on Resonance Light Nanoalloys, Metallic, Bimetallic, and Magnetic Nanoparticles in
Scattering of Noble Metal Nanoparticles; Pan Stanford Publishing Pte. Biomedical Applications. Phys. Chem. Chem. Phys. 2015, 17, 27981−
Ltd.: 2012; pp 157−180. 27995.
(62) Eustis, S.; El-Sayed, M. A. Why Gold Nanoparticles are More (83) Mendoza-Garcia, A.; Sun, S. Recent Advances in the High-
Precious than Pretty Gold: Noble Metal Surface Plasmon Resonance Temperature Chemical Synthesis of Magnetic Nanoparticles. Adv.
and its Enhancement of the Radiative and nonradiative Properties of Funct. Mater. 2016, 26, 3809−3817.
Nanocrystals of Different Shapes. Chem. Soc. Rev. 2006, 35, 209−217. (84) Moraes Silva, S.; Tavallaie, R.; Sandiford, L.; Tilley, R. D.;
(63) Haes, A. J.; Stuart, D. A.; Nie, S.; Van Duyne, R. P. Using Gooding, J. J. Gold Coated Magnetic Nanoparticles: from Preparation
Solution-Phase Nanoparticles, Surface-Confined Nanoparticle Arrays to Surface Modification for Analytical and Biomedical Applications.
and Single Nanoparticles as Biological Sensing Platforms. J. Fluoresc. Chem. Commun. 2016, 52, 7528−7540.
2004, 14, 355−367. (85) Tokarev, A.; Yatvin, J.; Trotsenko, O.; Locklin, J.; Minko, S.
(64) Hough, R.; Reich, M.; Noble, R. In Noble Metal Nanoparticles in Nanostructured Soft Matter with Magnetic Nanoparticles. Adv. Funct.
Ore Systems; Pan Stanford Publishing Pte. Ltd.: 2012; pp 141−167. Mater. 2016, 26, 3761−3782.

8252 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(86) Ulbrich, K.; Hola, K.; Subr, V.; Bakandritsos, A.; Tucek, J.; (110) Kay, B. D.; Hofmann-Sievert, R.; Castleman, A. W., Jr. A
Zboril, R. Targeted Drug Delivery with Polymers and Magnetic Molecular Beam Clectric Deflection Study of Clusters: Acid and Salt
Nanoparticles: Covalent and Noncovalent Approaches, Release Molecules in Microscopic Aqueous and Ammonia Clusters. Chem.
Control, and Clinical Studies. Chem. Rev. 2016, 116, 5338−5431. Phys. 1986, 102, 407−15.
(87) Arvizo, R.; Bhattacharya, R.; Mukherjee, P. Gold Nanoparticles: (111) Kimble, M. L.; Justes, D. R.; Moore, N. A.; Castleman, A. W.,
Opportunities and Challenges in Nanomedicine. Expert Opin. Drug Jr. In Elucidating Mechanistic Details of Catalytic Reactions Utilizing Gas
Delivery 2010, 7, 753−763. Phase Clusters; World Scientific Publishing Co. Pte. Ltd.: 2005; pp
(88) Dykman, L.; Khlebtsov, N. Gold Nanoparticles in Biomedical 127−134.
Applications: Recent Advances and Perspectives. Chem. Soc. Rev. 2012, (112) Wisniewski, E. S.; Leskiw, B. D.; Hurley, S. M.; Dermota, T. E.;
41, 2256−82. Hydutsky, D. P.; Knappenberger, K. L., Jr.; Hershberger, M. A.;
(89) Sperling, R. A.; Rivera Gil, P.; Zhang, F.; Zanella, M.; Parak, W. Castleman, A. W., Jr. In Dynamics of Gas Phase Clusters: Insights into
J. Biological Applications of Gold Nanoparticles. Chem. Soc. Rev. 2008, Size and Solvation Effects on Electronic Relaxation and Hydrogen
37, 1896−1908. Transfer; World Scientific Publishing Co. Pte. Ltd.: 2002; pp 21−41.
(90) Zeng, S.; Yong, K.-T.; Roy, I.; Dinh, X.-Q.; Yu, X.; Luan, F. A (113) Zemski, K. A.; Justes, D. R.; Castleman, A. W., Jr. Studies of
Review on Functionalized Gold Nanoparticles for Biosensing Metal Oxide Clusters: Elucidating Reactive Sites Responsible for the
Applications. Plasmonics 2011, 6, 491−506. Activity of Transition Metal Oxide Catalysts. J. Phys. Chem. B 2002,
(91) Hunt, L. B. The True Story of Purple of Cassius. Gold Bull. 106, 6136−6148.
1976, 9, 134−139. (114) Ziemann, P. J.; Castleman, A. W., Jr. Stabilities and Structures
(92) Sreeprasad, T.; Pradeep, T. Noble Metal Nanoparticles. In of Gas-Phase Magnesium Oxide Clusters. J. Chem. Phys. 1991, 94,
Springer Handbook of Nanomaterials; Vajtai, R., Ed.; Springer: Berlin, 718−28.
2013; pp 303−388. (115) Katakuse, I.; Ichihara, T.; Fujita, Y.; Matsuo, T.; Sakurai, T.;
(93) Faraday, M. The Bakerian Lecture: Experimental Relations of Matsuda, H. Mass Distributions of Copper, Silver and Gold Clusters
Gold (and Other Metals) to Light. Philosophical Transactions of the and Electronic Shell Structure. Int. J. Mass Spectrom. Ion Processes 1985,
Royal Society of London 1857, 147, 145−181. 67, 229−236.
(94) Pasteur, L. On the extension of the germ theory to the etiology (116) Wurth, W.; Martins, M. Chapter 12 Electronic Structure and
of certain common diseases. C. R. Acad. Sci. XC 1880, 1033−1044. Magnetic Properties of Small Deposited Transition Metal Clusters. In
(95) Frens, G.; Overbeek, J. T. G. Carey Lea’s Colloidal Silver. The Chemical Physics of Solid Surfaces; Woodruff, D. P., Ed.; Elsevier:
Kolloid Z. Z. Polym. 1969, 233, 922−929.
2007; Vol. 12, pp 471−485.
(96) Kim, J. S.; Kuk, E.; Yu, K. N.; Kim, J. H.; Park, S. J.; Lee, H. J.;
(117) Johnston, R. L. Atomic and Molecular Clusters; CRC Press:
Kim, S. H.; Park, Y. K.; Park, Y. H.; Hwang, C. Y.; Kim, Y. K.; Lee, Y.
2002. DOI: 10.1201/9781420055771.
S.; Jeong, D. H.; Cho, M. H. Antimicrobial Effects of Silver
(118) Baksi, A.; Pradeep, T.; Yoon, B.; Yannouleas, C.; Landman, U.
Nanoparticles. Nanomedicine 2007, 3, 95−101.
Bare Clusters Derived from Protein Templates: Au25+, Au38+ and
(97) Pal, S.; Tak, Y. K.; Song, J. M. Does the Antibacterial Activity of
Au102+. ChemPhysChem 2013, 14, 1272−1282.
Silver Nanoparticles Depend on the Shape of the Nanoparticle? A
(119) Baksi, A.; Pradeep, T. Noble Metal Alloy Clusters in the Gas
Study of the Gram-Negative Bacterium Escherichia coli. Appl. Environ.
Phase Derived from Protein Templates: Unusual Recognition of
Microbiol. 2007, 73, 1712−1720.
Palladium by Gold. Nanoscale 2013, 5, 12245−12254.
(98) Shahverdi, A. R.; Fakhimi, A.; Shahverdi, H. R.; Minaian, S.
(120) Häkkinen, H.; Abbet, S.; Sanchez, A.; Heiz, U.; Landman, U.
Synthesis and Effect of Silver Nanoparticles on the Antibacterial
Activity of Different Antibiotics Against Staphylococcus Aureus and Structural, Electronic, and Impurity-Doping Effects in Nanoscale
Escherichia Coli. Nanomedicine 2007, 3, 168−171. Chemistry: Supported Gold Nanoclusters. Angew. Chem., Int. Ed. 2003,
(99) Tolaymat, T. M.; El Badawy, A. M.; Genaidy, A.; Scheckel, K. 42, 1297−1300.
G.; Luxton, T. P.; Suidan, M. An Evidence-based Environmental (121) Arenz, M.; Landman, U.; Heiz, U. CO Combustion on
Perspective of Manufactured Silver Nanoparticle in SynthesIs and Supported Gold Clusters. ChemPhysChem 2006, 7, 1871−1879.
Applications: a Systematic Review and Critical Appraisal of Peer- (122) Harding, C.; Habibpour, V.; Kunz, S.; Farnbacher, A. N.-S.;
reviewed Scientific Papers. Sci. Total Environ. 2010, 408, 999−1006. Heiz, U.; Yoon, B.; Landman, U. Control and Manipulation of Gold
(100) Corma, A.; Garcia, H. Supported Gold Nanoparticles as Nanocatalysis: Effects of Metal Oxide Support Thickness and
Catalysts for Organic Reactions. Chem. Soc. Rev. 2008, 37, 2096−2126. Composition. J. Am. Chem. Soc. 2009, 131, 538−548.
(101) Stratakis, M.; Garcia, H. Catalysis by Supported Gold (123) Abbet, S.; Heiz, U.; Häkkinen, H.; Landman, U. CO Oxidation
Nanoparticles: Beyond Aerobic Oxidative Processes. Chem. Rev. on a Single Pd Atom Supported on Magnesia. Phys. Rev. Lett. 2001, 86,
2012, 112, 4469−4506. 5950−5953.
(102) Pradeep, T. Nano: The Essentials; Tata McGraw-Hill (124) Liu, C.; Yang, B.; Tyo, E.; Seifert, S.; DeBartolo, J.; von
Education: 2007. Issendorff, B.; Zapol, P.; Vajda, S.; Curtiss, L. A. Carbon Dioxide
(103) Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, Conversion to Methanol over Size-Selected Cu4 Clusters at Low
R. E. C60: Buckminsterfullerene. Nature 1985, 318, 162−163. Pressures. J. Am. Chem. Soc. 2015, 137, 8676−8679.
(104) de Heer, W. A. The Physics of Simple Metal Clusters: (125) Tyo, E. C.; Vajda, S. Catalysis by Clusters with Precise
Experimental Aspects and Simple Models. Rev. Mod. Phys. 1993, 65, Numbers of Atoms. Nat. Nanotechnol. 2015, 10, 577−588.
611−676. (126) Vajda, S.; White, M. G. Catalysis Applications of Size-Selected
(105) Cohen, M. L.; Chou, M. Y.; Knight, W. D.; De Heer, W. A. Cluster Deposition. ACS Catal. 2015, 5, 7152−7176.
Physics of Metal Clusters. J. Phys. Chem. 1987, 91, 3141−3149. (127) Lu, J.; Cheng, L.; Lau, K. C.; Tyo, E.; Luo, X.; Wen, J.; Miller,
(106) Castleman, A. W., Jr. Studies of Gas-phase Clusters: Application D.; Assary, R. S.; Wang, H.-H.; Redfern, P.; Wu, H.; Park, J.-B.; Sun,
to Nucleation and Aerosol Formation; Pennsylvania State University: Y.-K.; Vajda, S.; Amine, K.; Curtiss, L. A. Effect of the Size-Selective
1985; p 35. Silver Clusters on Lithium Peroxide Morphology in Lithium−Oxygen
(107) Castleman, A. W., Jr.; Keesee, R. G. Clusters: Properties and batteries. Nat. Commun. 2014, 5, 4895.
Formation. Annu. Rev. Phys. Chem. 1986, 37, 525−50. (128) Turkevich, J.; Stevenson, P. C.; Hillier, J. A Study of the
(108) Chen, Z. Y.; Castleman, A. W., Jr. Growth of Titanium Nitride: Nucleation and Growth Processes in the Synthesis of Colloidal Gold.
from Clusters to Microcrystals. J. Chem. Phys. 1993, 98, 231−5. Discuss. Faraday Soc. 1951, 11, 55−75.
(109) Kay, B. D.; Hermann, V.; Castleman, A. W., Jr. Studies of Gas (129) Albano, V. G.; Bellon, P. L.; Manassero, M.; Sansoni, M.
Phase Clusters: the Solvation of Nitric Acid in Microscopic Aqueous Intermetallic Pattern in Metal-Atom Clusters. Structural Studies on
Clusters. Chem. Phys. Lett. 1981, 80, 469−74. Au11X3(PR3)7 Species. J. Chem. Soc. D 1970, 1210−1211.

8253 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(130) Briant, C. E.; Theobald, B. R. C.; White, J. W.; Bell, L. K.; Structure Investigation of [Au5(dppmH)3(dppm)](NO3)2 and
Mingos, D. M. P.; Welch, A. J. Synthesis and X-ray Structural [Au13(dppmH)6](NO3)n. Recueil des Travaux Chimiques des Pays-Bas
Characterization of the Centred Icosahedral Gold Cluster Compound 1981, 100, 148−152.
[Aul3(PMe2Ph)10Cl2](PF6)3; the Realization of a Theoretical Pre- (147) Arratia-Perez, R.; Hernandez-Acevedo, L. Relativistic Elec-
diction. J. Chem. Soc., Chem. Commun. 1981, 201−202. tronic Structure of an Icosahedral Au12Pd cluster. Chem. Phys. Lett.
(131) Copley, R. C. B.; Mingos, D. M. P. Synthesis and 1999, 303, 641−648.
Characterization of the Centred Icosahedral Cluster Series (148) Li, J.; Wang, S.-G. Phosphane-Stabilized Gold Clusters:
[Au9MIB4Cl4(PMePh2)8][C2B9H12], where MIB= Au, Ag or Cu. J. Investigation of the Stability of [Au13(PMe2Ph)10Cl2]3+. J. Mol.
Chem. Soc., Dalton Trans. 1996, 491−500. Model. 2010, 16, 505−512.
(132) Frens, G. Particle Size and Sol Stability in Metal Colloids. (149) Shafai, G.; Hong, S.; Bertino, M.; Rahman, T. S. Effect of
Kolloid Z. Z. Polym. 1972, 250, 736−741. Ligands on the Geometric and Electronic Structure of Au13 Clusters. J.
(133) McPartlin, M.; Mason, R.; Malatesta, L. Novel Cluster Phys. Chem. C 2009, 113, 12072−12078.
Complexes of Gold(0)-Gold(I). J. Chem. Soc. D 1969, 0, 334−334. (150) Shichibu, Y.; Suzuki, K.; Konishi, K. Facile Synthesis and
(134) Bellon, P.; Manassero, M.; Sansoni, M. Crystal and Molecular Optical Properties of Magic-Number Au13 Clusters. Nanoscale 2012, 4,
Structure of Tri-iodoheptakis(tri-p-fluorophenylphosphine)- 4125−4129.
undecagold. J. Chem. Soc., Dalton Trans. 1972, 1481−1487. (151) Shichibu, Y.; Konishi, K. HCl-Induced Nuclearity Convergence
(135) Briant, O. E.; Hall, K. P.; Mingos, D. M. P. Unusual in Diphosphine-Protected Ultrasmall Gold Clusters: A Novel
Degradation Reaction of Icosahedral Cluster Compounds of Gold with Synthetic Route to “Magic-Number” Au13 Clusters. Small 2010, 6,
Chelating Diphosphanes and the X-ray Structure of dis- 1216−1220.
(dephenylphosphino)methanido-digold(I), {Au(Ph2P)2CH}2. J. Orga- (152) Chen, J.; Zhang, Q.-F.; Williard, P. G.; Wang, L.-S. Synthesis
nomet. Chem. 1982, 229, C5−C8. and Structure Determination of a New Au20 Nanocluster Protected by
(136) Demartin, F.; Manassero, M.; Naldini, L.; Ruggeri, R.; Sansoni, Tripodal Tetraphosphine Ligands. Inorg. Chem. 2014, 53, 3932−3934.
M. Synthesis and X-ray Characterization of an Iodine-bridged (153) Teo, B. K.; Shi, X.; Zhang, H. Pure Gold Cluster of
Tetranuclear Gold Cluster, di-[small micro]-iodo-tetrakis- 1:9:9:1:9:9:1 Layered Structure: a Novel 39-Metal-Atom Cluster
(triphenylphosphine)-tetrahedro-tetragold. J. Chem. Soc., Chem. [(Ph3P)14Au39Cl6]Cl2 with an Interstitial Gold Atom in a Hexagonal
Commun. 1981, 222−223. Antiprismatic Cage. J. Am. Chem. Soc. 1992, 114, 2743−2745.
(137) van der Velden, J. W. A.; Bour, J. J.; Vollenbroek, F. A.; (154) Teo, B. K.; Zhang, H.; Shi, X. Molecular Architecture of a
Beurskens, P. T.; Smits, J. M. M. Synthesis of a New Pentanuclear Novel Vertex-Sharing Biicosahedral Cluster [(p-Tol3P)10Au13Ag12Br8]-
Gold cluster by Metal Evaporation. Preparation and X-ray structure (PF6) Containing a Staggered-Staggered-Staggered Configuration for
Determination of [tris{bis(diphenylphosphino)methane}][bis- the 25-Atom Metal Framework. Inorg. Chem. 1990, 29, 2083−2091.
(diphenylphosphino)methanido]pentagold Dinitrate. J. Chem. Soc., (155) Teo, B. K.; Zhang, H.; Shi, X. Cluster of Clusters: a Modular
Chem. Commun. 1979, 1162−1163. Approach to Large Metal Clusters. Structural Characterization of a 38-
(138) Briant, C. E.; Hall, K. P.; Mingos, D. M. P. Synthesis and atom Cluster [(p-Tol3P)12Au18Ag20Cl14] Based on Vertex-sharing
Structural Characterisation of [Au6(PPh3)6]− (NO3)2·3CH2Cl2; an Triicosahedra. J. Am. Chem. Soc. 1990, 112, 8552−8562.
Edge-shared Bitetrahedral Gold Cluster. J. Organomet. Chem. 1983, (156) Teo, B. K.; Zhang, H.; Shi, X. Site Preference in Vertex-Sharing
254, C18−C20. Polyicosahedral Supraclusters Containing Groups 10 and 11 Metals
(139) Briant, C. E.; Hall, K. P.; Mingos, D. M. P.; Wheeler, A. C. and Their Bonding Implications: Syntheses and Structures of the First
Synthesis and Structural Characterisation of Hexakis(triphenyl Au-Ag-M (M = Pt, Ni) Biicosahedral Clusters
phosphine)hexagold(2+) nitrate, [Au6(PPh3)6][NO3]2, and Related [(Ph3P)10Au12Ag12PtCl7]Cl and [(Ph3P)10Au12Ag12NiCl7](SbF6).
Clusters with Edgesharing Bitetrahedral Geometries. J. Chem. Soc., Inorg. Chem. 1994, 33, 4086−4097.
Dalton Trans. 1986, 687−692. (157) Schmid, G.; Pugin, R.; Meyer-Zaika, W.; Simon, U. Clusters on
(140) Van der Velden, J. W. A.; Beurskens, P. T.; Bour, J. J.; Bosman, Clusters: closo-Dodecaborate as a Ligand for Au55 Clusters. Eur. J.
W. P.; Noordik, J. H.; Kolenbrander, M.; Buskes, J. A. K. M. Inorg. Chem. 1999, 1999, 2051−2055.
Intermediates in the Formation of Gold Clusters. Preparation and X- (158) Maoz, R.; Cohen, S. R.; Sagiv, J. Nanoelectrochemical
ray Analysis of [Au7(PPh3)7]+ and Synthesis and Characterization of Patterning of Monolayer Surfaces: Toward Spatially Defined Self-
[Au8(PPh3)6I]PF6. Inorg. Chem. 1984, 23, 146−151. Assembly of Nanostructures. Adv. Mater. 1999, 11, 55−61.
(141) Weinberger, D. S.; Melaimi, M.; Moore, C. E.; Rheingold, A. (159) Vidoni, O.; Reuter, T.; Torma, V.; Meyer-Zaika, W.; Schmid,
L.; Frenking, G.; Jerabek, P.; Bertrand, G. Isolation of Neutral Mono- G. Quasi One-Dimensional Gold Cluster Arrangements. J. Mater.
and Dinuclear Gold Complexes of Cyclic (Alkyl) (amino)carbenes. Chem. 2001, 11, 3188−3190.
Angew. Chem., Int. Ed. 2013, 52, 8964−8967. (160) Schmid, G.; Bäumle, M.; Beyer, N. Ordered Two-Dimensional
(142) Zeller, E.; Beruda, H.; Schmidbaur, H. Tetrahedral Gold Monolayers of Au55 Clusters. Angew. Chem., Int. Ed. 2000, 39, 181−
Cluster [Au4]2+: Crystal structure of [(tert- 183.
Bu)3PAu]4(BF4−)2.2CHCl3. Inorg. Chem. 1993, 32, 3203−3204. (161) Schmid, G.; Pugin, R.; Sawitowski, T.; Simon, U.; Marler, B.
(143) van der Velden, J. W. A.; Bour, J. J.; Bosman, W. P.; Noordik, J. Transmission Electron Microscopic and Small angle X-ray Diffraction
H. Synthesis and X-ray Crystal Structure Determination of the Investigations of Au55(PPh3)12Cl6 Microcrystals[dagger]. Chem.
Cationic Gold Cluster Compound [Au8(PPh3)7](NO3)2. J. Chem. Soc., Commun. 1999, 1303−1304.
Chem. Commun. 1981, 1218−1219. (162) Schmid, G.; Baumle, M.; Geerkens, M.; Heim, I.; Osemann, C.;
(144) Bellon, P. L.; Cariati, F.; Manassero, M.; Naldini, L.; Sansoni, Sawitowski, T. Current and Future Applications of Nanoclusters.
M. Novel Gold clusters. Preparation, Properties, and X-ray Structure Chem. Soc. Rev. 1999, 28, 179−185.
Determination of Salts of octakis(triarylphosphine)enneagold, (163) Schmid, G.; Reuter, T.; Simon, U.; Noyong, M.; Blech, K.;
[Au9L8]X3. J. Chem. Soc. D 1971, 1423−1424. Santhanam, V.; Jäger, D.; Slomka, H.; Lüth, H.; Lepsa, M. I.
(145) Briant, C. E.; Hall, K. P.; Wheeler, A. C.; Mingos, D. M. P. Generation and Electrical Contacting of Gold Quantum Dots. Colloid
Structural Characterisation of [Au10Cl3(PCy2Ph)6](NO3) (Cy = Polym. Sci. 2008, 286, 1029−1037.
cyclohexyl) and the Development of a Structural Principle for High (164) Schmid, G.; Simon, U. Gold Nanoparticles: Assembly and
Nuclearity Gold Clusters. J. Chem. Soc., Chem. Commun. 1984, 248− Electrical Properties in 1−3 dimensions. Chem. Commun. 2005, 697−
250. 710.
(146) van der Velden, J. W. A.; Vollenbroek, F. A.; Bour, J. J.; (165) Simon, U.; Schön, G.; Schmid, G. The Application of Au55
Beurskens, P. T.; Smits, J. M. M.; Bosnian, W. P. Gold Clusters Clusters as Quantum Dots. Angew. Chem., Int. Ed. Engl. 1993, 32, 250−
Containing Bidentate Phosphine Ligands. Preparation and X-Ray 254.

8254 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(166) Torma, V.; Reuter, T.; Vidoni, O.; Schumann, M.; Radehaus, (186) Wu, Z.; Suhan, J.; Jin, R. One-pot Synthesis of Atomically
C.; Schmid, G. The Diode Behavior of Asymmetrically Ordered Au55 Monodisperse, Thiol-Functionalized Au25 Nanoclusters. J. Mater.
Clusters. ChemPhysChem 2001, 2, 546−548. Chem. 2009, 19, 622−626.
(167) Torma, V.; Schmid, G.; Simon, U. Structure−Property (187) Maity, P.; Xie, S.; Yamauchi, M.; Tsukuda, T. Stabilized Gold
Relations in Au55 Cluster Layers Studied by Temperature-Dependent Clusters: from Isolation Toward Controlled Synthesis. Nanoscale
Impedance Measurements. ChemPhysChem 2001, 2, 321−325. 2012, 4, 4027−4037.
(168) Zhang, H.; Hartmann, U.; Schmid, G. Energy-Level Splitting of (188) Duan, H.; Nie, S. Etching Colloidal Gold Nanocrystals with
Ligand-Stabilized Au55 Clusters Observed by Scanning Tunneling Hyperbranched and Multivalent Polymers: A New Route to
Spectroscopy. Appl. Phys. Lett. 2004, 84, 1543−1545. Fluorescent and Water-Soluble Atomic Clusters. J. Am. Chem. Soc.
(169) Qian, H.; Jin, R. Synthesis and Electrospray Mass Spectrometry 2007, 129, 2412−2413.
Determination of Thiolate-Protected Au55(SR)31 Nanoclusters. Chem. (189) Qian, H.; Zhu, M.; Lanni, E.; Zhu, Y.; Bier, M. E.; Jin, R.
Commun. 2011, 47, 11462−11464. Conversion of Polydisperse Au Nanoparticles into Monodisperse Au25
(170) Tsunoyama, H.; Negishi, Y.; Tsukuda, T. Chromatographic Nanorods and Nanospheres. J. Phys. Chem. C 2009, 113, 17599−
Isolation of ″Missing″ Au55 Clusters Protected by Alkanethiolates. J. 17603.
Am. Chem. Soc. 2006, 128, 6036−6037. (190) Lin, C.-A. J.; Yang, T.-Y.; Lee, C.-H.; Huang, S. H.; Sperling, R.
(171) Vogel, W.; Rosner, B.; Tesche, B. Structural Investigations of A.; Zanella, M.; Li, J. K.; Shen, J.-L.; Wang, H.-H.; Yeh, H.-I.; Parak, W.
Gold (Au55) Organometallic Complexes by X-ray Powder Diffraction J.; Chang, W. H. Synthesis, Characterization, and Bioconjugation of
and Transmission Electron Microscopy. J. Phys. Chem. 1993, 97, Fluorescent Gold Nanoclusters toward Biological Labeling Applica-
11611−11616. tions. ACS Nano 2009, 3, 395−401.
(172) Rapoport, D. H.; Vogel, W.; Cölfen, H.; Schlögl, R. Ligand- (191) Mrudula, K. V.; Bhaskara Rao, T. U.; Pradeep, T. Interfacial
Stabilized Metal Clusters: Reinvestigation of the Structure of synthesis of Luminescent 7 kDa Silver Clusters. J. Mater. Chem. 2009,
“Au55[P(C6H5)3]12Cl6. J. Phys. Chem. B 1997, 101, 4175−4183. 19, 4335−4342.
(173) Wallenberg, L. R.; Bovin, J. O.; Schmid, G. On the Crystal (192) Yu, Y.; Luo, Z.; Yu, Y.; Lee, J. Y.; Xie, J. Observation of Cluster
Structure of Small Gold Crystals and Large Gold Clusters. Surf. Sci. Size Growth in CO-Directed Synthesis of Au25(SR)18 Nanoclusters.
1985, 156, 256−264. ACS Nano 2012, 6, 7920−7927.
(174) Wang, Z. W.; Palmer, R. E. Experimental Evidence for (193) Chakraborty, I.; Bhuin, R. G.; Bhat, S.; Pradeep, T. Blue
Fluctuating, Chiral-Type Au55 Clusters by Direct Atomic Imaging. Emitting Undecaplatinum Cluster. Nanoscale 2014, 6, 8561−8564.
Nano Lett. 2012, 12, 5510−5514. (194) Chakraborty, I.; Erusappan, J.; Govindarajan, A.; Sugi, K. S.;
(175) Jian, N.; Stapelfeldt, C.; Hu, K.-J.; Froba, M.; Palmer, R. E. Udayabhaskararao, T.; Ghosh, A.; Pradeep, T. Emergence of
Hybrid Atomic Structure of the Schmid Cluster Au55(PPh3)12Cl6 Metallicity in Silver Clusters in the 150 Atom Regime: a Study of
Resolved by Aberration-Corrected STEM. Nanoscale 2015, 7, 885− Differently Sized Silver Clusters. Nanoscale 2014, 6, 8024−8031.
(195) Ganguly, A.; Chakraborty, I.; Udayabhaskararao, T.; Pradeep,
888.
T. A Copper Cluster Protected with Phenylethanethiol. J. Nanopart.
(176) Schmid, G.; Pfeil, R.; Boese, R.; Bandermann, F.; Meyer, S.;
Res. 2013, 15, 1522.
Calis, G. H. M.; van der Velden, J. W. A. Au55[P(C6H5)3]12Cl6  ein
(196) Sarkar, S.; Chakraborty, I.; Panwar, M. K.; Pradeep, T.
Goldcluster ungewöhnlicher Grösse. Chem. Ber. 1981, 114, 3634−
Isolation and Tandem Mass Spectrometric Identification of a Stable
3642.
Monolayer Protected Silver−Palladium Alloy Cluster. J. Phys. Chem.
(177) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R.
Lett. 2014, 5, 3757−3762.
Synthesis of Thiol-Derivatised Gold Nanoparticles in a Two-phase
(197) Kurashige, W.; Munakata, K.; Nobusada, K.; Negishi, Y.
Liquid-Liquid System. J. Chem. Soc., Chem. Commun. 1994, 0, 801− Synthesis of Stable CunAu25‑n Nanoclusters (n = 1−9) using Selenolate
802. Ligands. Chem. Commun. 2013, 49, 5447−5449.
(178) Perala, S. R. K.; Kumar, S. On the Mechanism of Metal (198) Negishi, Y.; Kurashige, W.; Niihori, Y.; Iwasa, T.; Nobusada, K.
Nanoparticle Synthesis in the Brust−Schiffrin Method. Langmuir Isolation, Structure, and Stability of a Dodecanethiolate-Protected
2013, 29, 9863−9873. Pd1Au24 Cluster. Phys. Chem. Chem. Phys. 2010, 12, 6219−6225.
(179) Branham, M. R.; Douglas, A. D.; Mills, A. J.; Tracy, J. B.; (199) Qian, H.; Jiang, D.-e.; Li, G.; Gayathri, C.; Das, A.; Gil, R. R.;
White, P. S.; Murray, R. W. Arylthiolate-Protected Silver Quantum Jin, R. Monoplatinum Doping of Gold Nanoclusters and Catalytic
Dots. Langmuir 2006, 22, 11376−11383. Application. J. Am. Chem. Soc. 2012, 134, 16159−16162.
(180) Devadas, M. S.; Kwak, K.; Park, J.-W.; Choi, J.-H.; Jun, C.-H.; (200) Shichibu, Y.; Negishi, Y.; Tsunoyama, H.; Kanehara, M.;
Sinn, E.; Ramakrishna, G.; Lee, D. Directional Electron Transfer in Teranishi, T.; Tsukuda, T. Extremely High Stability of Glutathionate-
Chromophore-Labeled Quantum-Sized Au25 Clusters: Au25 as an Protected Au25 Clusters Against Core Etching. Small 2007, 3, 835−
Electron Donor. J. Phys. Chem. Lett. 2010, 1, 1497−1503. 839.
(181) Song, Y.; Harper, A. S.; Murray, R. W. Ligand Heterogeneity (201) Dhanalakshmi, L.; Udayabhaskararao, T.; Pradeep, T.
on Monolayer-Protected Gold Clusters. Langmuir 2005, 21, 5492− Conversion of Double Layer Charge-Stabilized Ag@citrate Colloids
5500. to Thiol Passivated Luminescent Quantum Clusters. Chem. Commun.
(182) Venzo, A.; Antonello, S.; Gascón, J. A.; Guryanov, I.; Leapman, 2012, 48, 859−861.
R. D.; Perera, N. V.; Sousa, A.; Zamuner, M.; Zanella, A.; Maran, F. (202) Shimizu, T.; Teranishi, T.; Hasegawa, S.; Miyake, M. Size
Effect of the Charge State (z = −1, 0, + 1) on the Nuclear Magnetic Evolution of Alkanethiol-Protected Gold Nanoparticles by Heat
Resonance of Monodisperse Au25[S(CH2)2Ph]18z Clusters. Anal. Treatment in the Solid State. J. Phys. Chem. B 2003, 107, 2719−2724.
Chem. 2011, 83, 6355−6362. (203) Gaur, S.; Miller, J. T.; Stellwagen, D.; Sanampudi, A.; Kumar,
(183) Goulet, P. J. G.; Lennox, R. B. New Insights into Brust− C. S. S. R.; Spivey, J. J. Synthesis, Characterization, and Testing of
Schriffin Metal Nanoparticle Synthesis. J. Am. Chem. Soc. 2010, 132, Supported Au Catalysts Prepared from Atomically-Tailored
9582−9584. Au38(SC12H25)24 Clusters. Phys. Chem. Chem. Phys. 2012, 14, 1627−
(184) Li, Y.; Zaluzhna, O.; Xu, B.; Gao, Y.; Modest, J. M.; Tong, Y. J. 1634.
Mechanistic Insights into the Brust−Schiffrin Two-Phase Synthesis of (204) Qian, H.; Eckenhoff, W. T.; Zhu, Y.; Pintauer, T.; Jin, R. Total
Organo-Chalcogenate-Protected Metal Nanoparticles. J. Am. Chem. Structure Determination of Thiolate-Protected Au38 Nanoparticles. J.
Soc. 2011, 133, 2092−2095. Am. Chem. Soc. 2010, 132, 8280−8281.
(185) Zhu, M.; Lanni, E.; Garg, N.; Bier, M. E.; Jin, R. Kinetically (205) Zheng, J.; Dickson, R. M. Individual Water-Soluble Dendrimer-
Controlled, High-Yield Synthesis of Au25 Clusters. J. Am. Chem. Soc. Encapsulated Silver Nanodot Fluorescence. J. Am. Chem. Soc. 2002,
2008, 130, 1138−1139. 124, 13982−13983.

8255 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(206) Liu, T.; Su, Y.; Song, H.; Lv, Y. Microwave-assisted Green (226) Cleveland, C. L.; Landman, U.; Shafigullin, M. N.; Stephens, P.
Synthesis of Ultrasmall Fluorescent Water-soluble Silver Nanoclusters W.; Whetten, R. L. Structural Evolution of Larger Gold Clusters. Z.
and its Application in Chiral Recognition of Amino Acids. Analyst Phys. D: At., Mol. Clusters 1997, 40, 503−508.
2013, 138, 6558−6564. (227) Schaaff, T. G.; Knight, G.; Shafigullin, M. N.; Borkman, R. F.;
(207) Ershov, B. G.; Henglein, A. Time-Resolved Investigation of Whetten, R. L. Isolation and Selected Properties of a 10.4 kDa
Early Processes in the Reduction of Ag+ on Polyacrylate in Aqueous Gold:Glutathione Cluster Compound. J. Phys. Chem. B 1998, 102,
Solution. J. Phys. Chem. B 1998, 102, 10667−10671. 10643−10646.
(208) Linnert, T.; Mulvaney, P.; Henglein, A.; Weller, H. Long-lived (228) Ingram, R. S.; Hostetler, M. J.; Murray, R. W. Poly-hetero-ω-
Nonmetallic Silver Clusters in Aqueous Solution: Preparation and functionalized Alkanethiolate-Stabilized Gold Cluster Compounds. J.
Photolysis. J. Am. Chem. Soc. 1990, 112, 4657−4664. Am. Chem. Soc. 1997, 119, 9175−9178.
(209) Ledo-Suárez, A.; Rivas, J.; Rodríguez-Abreu, C. F.; Rodríguez, (229) Negishi, Y.; Nobusada, K.; Tsukuda, T. Glutathione-Protected
M. J.; Pastor, E.; Hernández-Creus, A.; Oseroff, S. B.; López-Quintela, Gold Clusters Revisited: Bridging the Gap between Gold(I) Thiolate
M. A. Facile Synthesis of Stable Subnanosized Silver Clusters in Complexes and Thiolate-Protected Gold Nanocrystals. J. Am. Chem.
Microemulsions. Angew. Chem., Int. Ed. 2007, 46, 8823−8827. Soc. 2005, 127, 5261−5270.
(210) Xu, H.; Suslick, K. S. Sonochemical Synthesis of Highly (230) Yao, H.; Miki, K.; Nishida, N.; Sasaki, A.; Kimura, K. Large
Optical Activity of Gold Nanocluster Enantiomers Induced by a Pair of
Fluorescent Ag Nanoclusters. ACS Nano 2010, 4, 3209−3214.
Optically Active Penicillamines. J. Am. Chem. Soc. 2005, 127, 15536−
(211) Vilar-Vidal, N.; Blanco, M. C.; López-Quintela, M. A.; Rivas, J.;
15543.
Serra, C. Electrochemical Synthesis of Very Stable Photoluminescent
(231) Häkkinen, H.; Walter, M.; Grönbeck, H. Divide and Protect:
Copper Clusters. J. Phys. Chem. C 2010, 114, 15924−15930.
Capping Gold Nanoclusters with Molecular Gold−Thiolate Rings. J.
(212) Adhikari, B.; Banerjee, A. Facile Synthesis of Water-Soluble
Phys. Chem. B 2006, 110, 9927−9931.
Fluorescent Silver Nanoclusters and HgII Sensing. Chem. Mater. 2010, (232) Natarajan, G.; Mathew, A.; Negishi, Y.; Whetten, R. L.;
22, 4364−4371. Pradeep, T. A Unified Framework for Understanding the Structure
(213) Xie, J.; Zheng, Y.; Ying, J. Y. Protein-Directed Synthesis of and Modifications of Atomically Precise Monolayer Protected Gold
Highly Fluorescent Gold Nanoclusters. J. Am. Chem. Soc. 2009, 131, Clusters. J. Phys. Chem. C 2015, 119, 27768−27785.
888−889. (233) Krishnadas, K. R.; Ghosh, A.; Baksi, A.; Chakraborty, I.;
(214) Xavier, P. L.; Chaudhari, K.; Verma, P. K.; Pal, S. K.; Pradeep, Natarajan, G.; Pradeep, T. Intercluster Reactions between Au25(SR)18
T. Luminescent Quantum Clusters of Gold in Transferrin Family and Ag44(SR)30. J. Am. Chem. Soc. 2016, 138, 140−148.
Protein, Lactoferrin Exhibiting FRET. Nanoscale 2010, 2, 2769−2776. (234) Gross, D. H. E.; Madjet, M. E. Fragmentation Phase Transition
(215) Muhammed, M. A.; Aldeek, F.; Palui, G.; Trapiella-Alfonso, L.; in Atomic Clusters. IV. Liquid-gas Transition in Finite Metal Clusters
Mattoussi, H. Growth of in situ Functionalized Luminescent Silver and in the Bulk. Z. Phys. B: Condens. Matter 1997, 104, 541−551.
Nanoclusters by Direct Reduction and Size Focusing. ACS Nano 2012, (235) Knight, W. D.; Clemenger, K.; de Heer, W. A.; Saunders, W.
6, 8950−8961. A.; Chou, M. Y.; Cohen, M. L. Electronic Shell Structure and
(216) Chakraborty, I.; Udayabhaskararao, T.; Pradeep, T. Lumines- Abundances of Sodium Clusters. Phys. Rev. Lett. 1984, 52, 2141−2143.
cent Sub-nanometer Clusters for Metal Ion Sensing: A New Direction (236) Morse, M. D. Clusters of transition-metal atoms. Chem. Rev.
in Nanosensors. J. Hazard. Mater. 2012, 211−212, 396−403. 1986, 86, 1049−1109.
(217) Yeh, H.-C.; Sharma, J.; Han, J. J.; Martinez, J. S.; Werner, J. H. (237) O’Hair, R. J.; Khairallah, G. Gas Phase Ion Chemistry of
A DNA−Silver Nanocluster Probe That Fluoresces upon Hybrid- Transition Metal Clusters: Production, Reactivity, and Catalysis. J.
ization. Nano Lett. 2010, 10, 3106−3110. Cluster Sci. 2004, 15, 331−363.
(218) Chakraborty, I.; Mahata, S.; Mitra, A.; De, G.; Pradeep, T. (238) Singh, D. M. D. J.; Pradeep, T.; Bhattacharjee, J.; Waghmare,
Controlled Synthesis and Characterization of the Elusive Thiolated U. V. Novel Cage Clusters of MoS2 in the Gas Phase. J. Phys. Chem. A
Ag55 Cluster. Dalton Trans. 2014, 43, 17904−17907. 2005, 109, 7339−7342.
(219) Ghosh, A.; Udayabhaskararao, T.; Pradeep, T. One-Step Route (239) Singh, D. M. D. J.; Pradeep, T.; Bhattacharjee, J.; Waghmare,
to Luminescent Au18SG14 in the Condensed Phase and Its Closed U. V. Closed-Cage Clusters in the Gaseous and Condensed Phases
Shell Molecular Ions in the Gas Phase. J. Phys. Chem. Lett. 2012, 3, Derived from Sonochemically Synthesized MoS2 Nanoflakes. J. Am.
1997−2002. Soc. Mass Spectrom. 2007, 18, 2191−2197.
(220) Chakraborty, I.; Pradeep, T. Reversible Formation of Ag44 from (240) Bhat, S.; Chakraborty, I.; Baksi, A.; Narayanan, R. P.; Pradeep,
Selenolates. Nanoscale 2014, 6, 14190−14194. T. Evolution of Atomically Precise Clusters through the Eye of Mass
(221) AbdulHalim, L. G.; Ashraf, S.; Katsiev, K.; Kirmani, A. R.; Spectrometry. Nanoscience 2016, 3, 343−385.
Kothalawala, N.; Anjum, D. H.; Abbas, S.; Amassian, A.; Stellacci, F.; (241) Ingram, R. S.; Hostetler, M. J.; Murray, R. W.; Schaaff, T. G.;
Khoury, J. T.; Whetten, R. L.; Bigioni, T. P.; Guthrie, D. K.; First, P. N.
Dass, A.; Hussain, I.; Bakr, O. M. A Scalable Synthesis of Highly Stable
28 kDa Alkanethiolate-Protected Au Clusters Give Analogous Solution
and Water Dispersible Ag44(SR)30 Nanoclusters. J. Mater. Chem. A
Electrochemistry and STM Coulomb Staircases. J. Am. Chem. Soc.
2013, 1, 10148−10154.
1997, 119, 9279−9280.
(222) Yang, H.; Wang, Y.; Huang, H.; Gell, L.; Lehtovaara, L.;
(242) Logunov, S. L.; Ahmadi, T. S.; El-Sayed, M. A.; Khoury, J. T.;
Malola, S.; Hakkinen, H.; Zheng, N. All-thiol-stabilized Ag44 and Whetten, R. L. Electron Dynamics of Passivated Gold Nanocrystals
Au12Ag32 Nanoparticles with Single-crystal Structures. Nat. Commun. Probed by Subpicosecond Transient Absorption Spectroscopy. J. Phys.
2013, 4, 2422. Chem. B 1997, 101, 3713−3719.
(223) Whetten, R. L.; Khoury, J. T.; Alvarez, M. M.; Murthy, S.; (243) Schaaff, T. G.; Shafigullin, M. N.; Khoury, J. T.; Vezmar, I.;
Vezmar, I.; Wang, Z. L.; Stephens, P. W.; Cleveland, C. L.; Luedtke, Whetten, R. L.; Cullen, W. G.; First, P. N.; Gutiérrez-Wing, C.;
W. D.; Landman, U. Nanocrystal Gold Molecules. Adv. Mater. 1996, 8, Ascensio, J.; Jose-Yacamán, M. J. Isolation of Smaller Nanocrystal Au
428−433. Molecules: Robust Quantum Effects in Optical Spectra. J. Phys. Chem.
(224) Cleveland, C. L.; Landman, U.; Schaaff, T. G.; Shafigullin, M. B 1997, 101, 7885−7891.
N.; Stephens, P. W.; Whetten, R. L. Structural Evolution of Smaller (244) Schaaff, T. G.; Whetten, R. L. Giant Gold-Glutathione Cluster
Gold Nanocrystals: The Truncated Decahedral Motif. Phys. Rev. Lett. Compounds: Intense Optical Activity in Metal-Based Transitions. J.
1997, 79, 1873−1876. Phys. Chem. B 2000, 104, 2630−2641.
(225) Yannouleas, C.; Landman, U. Electronic Entropy, Shell (245) Templeton, A. C.; Cliffel, D. E.; Murray, R. W. Redox and
Structure, and Size-Evolutionary Patterns of Metal Clusters. Phys. Fluorophore Functionalization of Water-Soluble, Tiopronin-Protected
Rev. Lett. 1997, 78, 1424−1427. Gold Clusters. J. Am. Chem. Soc. 1999, 121, 7081−7089.

8256 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(246) Hicks, J. F.; Templeton, A. C.; Chen, S.; Sheran, K. M.; Jasti, (266) Varnavski, O.; Ramakrishna, G.; Kim, J.; Lee, D.; Goodson, T.
R.; Murray, R. W.; Debord, J.; Schaaff, T. G.; Whetten, R. L. The Critical Size for the Observation of Quantum Confinement in
Monolayer Thickness Dependence of Quantized Double-Layer Optically Excited Gold Clusters. J. Am. Chem. Soc. 2010, 132, 16−17.
Capacitances of Monolayer-Protected Gold Clusters. Anal. Chem. (267) Alvarez, M. M.; Khoury, J. T.; Schaaff, T. G.; Shafigullin, M.;
1999, 71, 3703−3711. Vezmar, I.; Whetten, R. L. Critical Sizes in the Growth of Au Clusters.
(247) Ingram, R. S.; Murray, R. W. Electroactive Three-Dimensional Chem. Phys. Lett. 1997, 266, 91−98.
Monolayers: Anthraquinone ω-Functionalized Alkanethiolate-Stabi- (268) Hostetler, M. J.; Wingate, J. E.; Zhong, C.-J.; Harris, J. E.;
lized Gold Clusters. Langmuir 1998, 14, 4115−4121. Vachet, R. W.; Clark, M. R.; Londono, J. D.; Green, S. J.; Stokes, J. J.;
(248) Schaaff, T. G.; Shafigullin, M. N.; Khoury, J. T.; Vezmar, I.; Wignall, G. D.; Glish, G. L.; Porter, M. D.; Evans, N. D.; Murray, R. W.
Whetten, R. L. Properties of a Ubiquitous 29 kDa Au:SR Cluster Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5
Compounds. J. Phys. Chem. B 2001, 105, 8785−8796. to 5.2 nm: Core and Monolayer Properties as a Function of Core Size.
(249) Link, S.; Beeby, A.; FitzGerald, S.; El-Sayed, M. A.; Schaaff, T. Langmuir 1998, 14, 17−30.
G.; Whetten, R. L. Visible to Infrared Luminescence from a 28-Atom (269) Miller, S. A.; Womick, J. M.; Parker, J. F.; Murray, R. W.;
Gold Cluster. J. Phys. Chem. B 2002, 106, 3410−3415. Moran, A. M. Femtosecond Relaxation Dynamics of Au25L18−
(250) Donkers, R. L.; Lee, D.; Murray, R. W. Synthesis and Isolation Monolayer-Protected Clusters. J. Phys. Chem. C 2009, 113, 9440−
of the Molecule-like Cluster Au38(PhCH2CH2S)24. Langmuir 2004, 20, 9444.
1945−1952. (270) Miller, S. A.; Fields-Zinna, C. A.; Murray, R. W.; Moran, A. M.
(251) Jimenez, V. L.; Georganopoulou, D. G.; White, R. J.; Harper, A. Nonlinear Optical Signatures of Core and Ligand Electronic States in
S.; Mills, A. J.; Lee, D.; Murray, R. W. Hexanethiolate Monolayer Au24PdL18. J. Phys. Chem. Lett. 2010, 1, 1383−1387.
Protected 38 Gold Atom Cluster. Langmuir 2004, 20, 6864−6870. (271) Qian, H.; Sfeir, M. Y.; Jin, R. Ultrafast Relaxation Dynamics of
(252) Lee, D.; Donkers, R. L.; Wang, G.; Harper, A. S.; Murray, R. [Au25(SR)18]q Nanoclusters: Effects of Charge State. J. Phys. Chem. C
W. Electrochemistry and Optical Absorbance and Luminescence of 2010, 114, 19935−19940.
Molecule-like Au38 Nanoparticles. J. Am. Chem. Soc. 2004, 126, 6193− (272) Varnavski, O.; Ramakrishna, G.; Kim, J.; Lee, D.; Goodson, T.
6199. Optically Excited Acoustic Vibrations in Quantum-Sized Monolayer-
(253) Bigioni, T. P.; Whetten, R. L.; Dag, Ö . Near-Infrared Protected Gold Clusters. ACS Nano 2010, 4, 3406−3412.
Luminescence from Small Gold Nanocrystals. J. Phys. Chem. B 2000, (273) Devadas, M. S.; Kim, J.; Sinn, E.; Lee, D.; Goodson, T.;
104, 6983−6986. Ramakrishna, G. Unique Ultrafast Visible Luminescence in Mono-
(254) Kimura, K.; Sugimoto, N.; Sato, S.; Yao, H.; Negishi, Y.; layer-Protected Au25 Clusters. J. Phys. Chem. C 2010, 114, 22417−
Tsukuda, T. Size Determination of Gold Clusters by Polyacrylamide 22423.
Gel Electrophoresis in a Large Cluster Region. J. Phys. Chem. C 2009, (274) Miles, D. T.; Murray, R. W. Temperature-Dependent
113, 14076−14082. Quantized Double Layer Charging of Monolayer-Protected Gold
(255) Negishi, Y.; Nakazaki, T.; Malola, S.; Takano, S.; Niihori, Y.; Clusters. Anal. Chem. 2003, 75, 1251−1257.
Kurashige, W.; Yamazoe, S.; Tsukuda, T.; Häkkinen, H. A Critical Size (275) Shibu, E. S.; Pradeep, T. Photoluminescence and Temperature-
for Emergence of Nonbulk Electronic and Geometric Structures in Dependent Emission Studies of Au25 Clusters In the Solid State. Int. J.
Dodecanethiolate-Protected Au Clusters. J. Am. Chem. Soc. 2015, 137, Nanosci. 2009, 08, 223−226.
1206−1212. (276) Devadas, M. S.; Bairu, S.; Qian, H.; Sinn, E.; Jin, R.;
(256) Niihori, Y.; Matsuzaki, M.; Uchida, C.; Negishi, Y. Advanced Ramakrishna, G. Temperature-Dependent Optical Absorption Proper-
Use of High-Performance Liquid Chromatography for Synthesis of ties of Monolayer-Protected Au25 and Au38 Clusters. J. Phys. Chem.
Controlled Metal Clusters. Nanoscale 2014, 6, 7889−7896. Lett. 2011, 2, 2752−2758.
(257) Knoppe, S.; Boudon, J.; Dolamic, I.; Dass, A.; Burgi, T. Size (277) Mooney, J.; Kambhampati, P. Correction to “Get the Basics
Exclusion Chromatography for Semipreparative Scale Separation of Right: Jacobian Conversion of Wavelength and Energy Scales for
Au38(SR)24 and Au40(SR)24 and Larger Clusters. Anal. Chem. 2011, 83, Quantitative Analysis of Emission Spectra. J. Phys. Chem. Lett. 2014, 5,
5056−5061. 3497−3497.
(258) Ghosh, A.; Hassinen, J.; Pulkkinen, P.; Tenhu, H.; Ras, R. H. (278) Luo, Z.; Yuan, X.; Yu, Y.; Zhang, Q.; Leong, D. T.; Lee, J. Y.;
A.; Pradeep, T. Simple and Efficient Separation of Atomically Precise Xie, J. From Aggregation-Induced Emission of Au(I)−Thiolate
Noble Metal Clusters. Anal. Chem. 2014, 86, 12185−12190. Complexes to Ultrabright Au(0)@Au(I)−Thiolate Core−Shell Nano-
(259) Zhu, Y.; Jin, R.; Sun, Y. Atomically Monodisperse Gold clusters. J. Am. Chem. Soc. 2012, 134, 16662−16670.
Nanoclusters Catalysts with Precise Core-shell Structure. Catalysts (279) Yuan, X.; Luo, Z.; Zhang, Q.; Zhang, X.; Zheng, Y.; Lee, J. Y.;
2011, 1, 3−17. Xie, J. Synthesis of Highly Fluorescent Metal (Ag, Au, Pt, and Cu)
(260) Jin, R.; Qian, H.; Wu, Z.; Zhu, Y.; Zhu, M.; Mohanty, A.; Garg, Nanoclusters by Electrostatically Induced Reversible Phase Transfer.
N. Size Focusing: A Methodology for Synthesizing Atomically Precise ACS Nano 2011, 5, 8800−8808.
Gold Nanoclusters. J. Phys. Chem. Lett. 2010, 1, 2903−2910. (280) Weerawardene, K. L. D. M.; Aikens, C. M. Theoretical Insights
(261) Negishi, Y.; Takasugi, Y.; Sato, S.; Yao, H.; Kimura, K.; into the Origin of Photoluminescence of Au25(SR)18− Nanoparticles. J.
Tsukuda, T. Magic-Numbered Aun Clusters Protected by Glutathione Am. Chem. Soc. 2016, 138, 11202−11210.
Monolayers (n = 18, 21, 25, 28, 32, 39): Isolation and Spectroscopic (281) Wu, Z.; Jin, R. On the Ligand’s Role in the Fluorescence of
Characterization. J. Am. Chem. Soc. 2004, 126, 6518−6519. Gold Nanoclusters. Nano Lett. 2010, 10, 2568−2573.
(262) Yu, Y.; Chen, X.; Yao, Q.; Yu, Y.; Yan, N.; Xie, J. Scalable and (282) Wang, S.; Zhu, X.; Cao, T.; Zhu, M. A Simple Model for
Precise Synthesis of Thiolated Au 10−12 , Au 15 , Au 18 , and Au 25 Understanding the Fluorescence Behavior of Au25 Nanoclusters.
Nanoclusters via pH Controlled CO Reduction. Chem. Mater. 2013, Nanoscale 2014, 6, 5777−5781.
25, 946−952. (283) Shibu, E. S.; Muhammed, M. A. H.; Tsukuda, T.; Pradeep, T.
(263) Yuan, X.; Zhang, B.; Luo, Z.; Yao, Q.; Leong, D. T.; Yan, N.; Ligand Exchange of Au25SG18 Leading to Functionalized Gold
Xie, J. Balancing the Rate of Cluster Growth and Etching for Gram- Clusters: Spectroscopy, Kinetics, and Luminescence. J. Phys. Chem.
Scale Synthesis of Thiolate-Protected Au25 Nanoclusters with Atomic C 2008, 112, 12168−12176.
Precision. Angew. Chem., Int. Ed. 2014, 53, 4623−4627. (284) van Wijngaarden, J. T.; Toikkanen, O.; Liljeroth, P.; Quinn, B.
(264) Yuan, X.; Yu, Y.; Yao, Q.; Zhang, Q.; Xie, J. Fast Synthesis of M.; Meijerink, A. Temperature-Dependent Emission of Monolayer-
Thiolated Au25 Nanoclusters via Protection−Deprotection Method. J. Protected Au38 Clusters. J. Phys. Chem. C 2010, 114, 16025−16028.
Phys. Chem. Lett. 2012, 3, 2310−2314. (285) Ciabatti, I.; Femoni, C.; Iapalucci, M. C.; Longoni, G.;
(265) Jin, R. Atomically Precise Metal Nanoclusters: Stable Sizes and Zacchini, S.; Zarra, S. Surface Decorated Platinum Carbonyl Clusters.
Optical Properties. Nanoscale 2015, 7, 1549−1565. Nanoscale 2012, 4, 4166−4177.

8257 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(286) Fresch, B.; Boyen, H. G.; Remacle, F. Magnetostructural tation: Au25(SCH2CH2Ph)18 and Mixed Monolayer
Effects in Ligand Stabilized Pd13 Clusters: a Density Functional Au25(SCH2CH2Ph)18−x(L)x. J. Am. Chem. Soc. 2008, 130, 5940−5946.
Theory Study. Nanoscale 2012, 4, 4138−4147. (307) Dass, A. Faradaurate Nanomolecules: A Superstable Plasmonic
(287) Green, T. D.; Knappenberger, K. L. Relaxation dynamics of 76.3 kDa Cluster. J. Am. Chem. Soc. 2011, 133, 19259−19261.
Au25L18 Nanoclusters Studied by Femtosecond Time-resolved Near (308) Dharmaratne, A. C.; Krick, T.; Dass, A. Nanocluster Size
Infrared Transient Absorption Spectroscopy. Nanoscale 2012, 4, Evolution Studied by Mass Spectrometry in Room Temperature
4111−4118. Au25(SR)18 Synthesis. J. Am. Chem. Soc. 2009, 131, 13604−13605.
(288) Gronbeck, H. The Bonding in Thiolate Protected Gold (309) Nimmala, P. R.; Yoon, B.; Whetten, R. L.; Landman, U.; Dass,
Nanoparticles from Au4f Photoemission Core Level Shifts. Nanoscale A. Au67(SR)35 Nanomolecules: Characteristic Size-Specific Optical,
2012, 4, 4178−4182. Electrochemical, Structural Properties and First-Principles Theoretical
(289) Jin, R.; Eah, S.-K.; Pei, Y. Quantum-sized Metal Nanoclusters. Analysis. J. Phys. Chem. A 2013, 117, 504−517.
Nanoscale 2012, 4, 4026−4026. (310) Krishnadas, K. R.; Baksi, A.; Ghosh, A.; Natarajan, G.; Pradeep,
(290) Martin, M. N.; Li, D.; Dass, A.; Eah, S.-K. Ultrafast, 2 min T. Structure-Conserving Spontaneous Transformations between
Synthesis of Monolayer-Protected Gold Nanoclusters (d < 2 nm). Nanoparticles. Nat. Commun. 2016, 7, 13447.
Nanoscale 2012, 4, 4091−4094. (311) Luo, Z.; Nachammai, V.; Zhang, B.; Yan, N.; Leong, D. T.;
(291) Meng, X.; Xu, Q.; Wang, S.; Zhu, M. Ligand-exchange Jiang, D.-e.; Xie, J. Toward Understanding the Growth Mechanism:
Synthesis of Selenophenolate-capped Au25 Nanoclusters. Nanoscale Tracing All Stable Intermediate Species from Reduction of Au(I)−
2012, 4, 4161−4165. Thiolate Complexes to Evolution of Au25 Nanoclusters. J. Am. Chem.
(292) Nambiar, S. R.; Aneesh, P. K.; Sukumar, C.; Rao, T. P. Mixed Soc. 2014, 136, 10577−10580.
Monolayer Protected Gold Atom-oxide Cluster Synthesis and (312) Fields-Zinna, C. A.; Sampson, J. S.; Crowe, M. C.; Tracy, J. B.;
Characterization. Nanoscale 2012, 4, 4130−4137. Parker, J. F.; deNey, A. M.; Muddiman, D. C.; Murray, R. W. Tandem
(293) Pei, Y.; Zeng, X. C. Investigating the Structural Evolution of Mass Spectrometry of Thiolate-Protected Au Nanoparticles
Thiolate Protected Gold Clusters from First-principles. Nanoscale NaxAu25(SC2H4Ph)18−y(S(C2H4O)5CH3)y. J. Am. Chem. Soc. 2009,
2012, 4, 4054−4072. 131, 13844−13851.
(294) Shang, L.; Yang, L.; Stockmar, F.; Popescu, R.; Trouillet, V.; (313) Chaki, N. K.; Negishi, Y.; Tsunoyama, H.; Shichibu, Y.;
Bruns, M.; Gerthsen, D.; Nienhaus, G. U. Microwave-assisted Rapid Tsukuda, T. Ubiquitous 8 and 29 kDa Gold:Alkanethiolate Cluster
Synthesis of Luminescent Gold Nanoclusters for Sensing Hg2+ in Compounds: Mass-Spectrometric Determination of Molecular For-
Living Cells Using Fluorescence Imaging. Nanoscale 2012, 4, 4155− mulas and Structural Implications. J. Am. Chem. Soc. 2008, 130, 8608−
4160. 8610.
(295) Sharma, J.; Rocha, R. C.; Phipps, M. L.; Yeh, H.-C.; Balatsky, (314) Angel, L. A.; Majors, L. T.; Dharmaratne, A. C.; Dass, A. Ion
K. A.; Vu, D. M.; Shreve, A. P.; Werner, J. H.; Martinez, J. S. A DNA- Mobility Mass Spectrometry of Au25(SCH2CH2Ph)18 Nanoclusters.
templated Fluorescent Silver Nanocluster with Enhanced Stability. ACS Nano 2010, 4, 4691−4700.
Nanoscale 2012, 4, 4107−4110. (315) Chen, S.; Wang, S.; Zhong, J.; Song, Y.; Zhang, J.; Sheng, H.;
(296) Tang, Z.; Ahuja, T.; Wang, S.; Wang, G. Near Infrared Pei, Y.; Zhu, M. The Structure and Optical Properties of the
Luminescence of Gold Nanoclusters Affected by the Bonding of 1,4- [Au18(SR)14] Nanocluster. Angew. Chem., Int. Ed. 2015, 54, 3145−
dithiolate Durene and Monothiolate Phenylethanethiolate. Nanoscale 3149.
2012, 4, 4119−4124. (316) Das, A.; Liu, C.; Byun, H. Y.; Nobusada, K.; Zhao, S.; Rosi, N.;
(297) Wang, L.-M.; Wang, L.-S. Probing the Electronic Properties Jin, R. Structure Determination of [Au18(SR)14]. Angew. Chem., Int. Ed.
and Structural Evolution of Anionic Gold Clusters in the Gas Phase. 2015, 54, 3140−3144.
Nanoscale 2012, 4, 4038−4053. (317) Zeng, C.; Liu, C.; Chen, Y.; Rosi, N. L.; Jin, R. Gold−Thiolate
(298) Wang, M.; Wu, Z.; Yang, J.; Wang, G.; Wang, H.; Cai, W. Ring as a Protecting Motif in the Au20(SR)16 Nanocluster and
Au25(SG)18 as a Fluorescent Iodide Sensor. Nanoscale 2012, 4, 4087− Implications. J. Am. Chem. Soc. 2014, 136, 11922−11925.
4090. (318) Das, A.; Li, T.; Nobusada, K.; Zeng, C.; Rosi, N. L.; Jin, R.
(299) Wong, O. A.; Heinecke, C. L.; Simone, A. R.; Whetten, R. L.; Nonsuperatomic [Au23(SC6H11)16]− Nanocluster Featuring Bipyrami-
Ackerson, C. J. Ligand Symmetry-equivalence on Thiolate Protected dal Au15 Kernel and Trimeric Au3(SR)4 Motif. J. Am. Chem. Soc. 2013,
Gold Nanoclusters Determined by NMR Spectroscopy. Nanoscale 135, 18264−18267.
2012, 4, 4099−4102. (319) Crasto, D.; Barcaro, G.; Stener, M.; Sementa, L.; Fortunelli, A.;
(300) Yamamoto, H.; Yano, H.; Kouchi, H.; Obora, Y.; Arakawa, R.; Dass, A. Au24(SAdm)16 Nanomolecules: X-ray Crystal Structure,
Kawasaki, H. N,N-Dimethylformamide-stabilized Gold Nanoclusters Theoretical Analysis, Adaptability of Adamantane Ligands to Form
as a Catalyst for the Reduction of 4-Nitrophenol. Nanoscale 2012, 4, Au23(SAdm)16 and Au25(SAdm)16, and Its Relation to Au25(SR)18. J.
4148−4154. Am. Chem. Soc. 2014, 136, 14933−14940.
(301) Zheng, J.; Zhou, C.; Yu, M.; Liu, J. Different Sized (320) Zeng, C.; Li, T.; Das, A.; Rosi, N. L.; Jin, R. Chiral Structure of
Luminescent Gold Nanoparticles. Nanoscale 2012, 4, 4073−4083. Thiolate-Protected 28-Gold-Atom Nanocluster Determined by X-ray
(302) Zhou, T.; Rong, M.; Cai, Z.; Yang, C. J.; Chen, X. Crystallography. J. Am. Chem. Soc. 2013, 135, 10011−10013.
Sonochemical Synthesis of Highly Fluorescent Glutathione-Stabilized (321) Crasto, D.; Malola, S.; Brosofsky, G.; Dass, A.; Häkkinen, H.
Ag Nanoclusters and S2‑ sensing. Nanoscale 2012, 4, 4103−4106. Single Crystal XRD Structure and Theoretical Analysis of the Chiral
(303) Fields-Zinna, C. A.; Crowe, M. C.; Dass, A.; Weaver, J. E. F.; Au30S(S-t-Bu)18 Cluster. J. Am. Chem. Soc. 2014, 136, 5000−5005.
Murray, R. W. Mass Spectrometry of Small Bimetal Monolayer- (322) Zeng, C.; Chen, Y.; Liu, C.; Nobusada, K.; Rosi, N. L.; Jin, R.
Protected Clusters. Langmuir 2009, 25, 7704−7710. Gold Tetrahedra Coil up: Kekulé-like and Double Helical Super-
(304) Tracy, J. B.; Kalyuzhny, G.; Crowe, M. C.; Balasubramanian, structures. Sci. Adv. 2015, 1, e1500425.
R.; Choi, J.-P.; Murray, R. W. Poly(ethylene glycol) Ligands for High- (323) Zeng, C.; Liu, C.; Chen, Y.; Rosi, N. L.; Jin, R. Atomic
Resolution Nanoparticle Mass Spectrometry. J. Am. Chem. Soc. 2007, Structure of Self-Assembled Monolayer of Thiolates on a Tetragonal
129, 6706−6707. Au92 Nanocrystal. J. Am. Chem. Soc. 2016, 138, 8710−8713.
(305) Negishi, Y.; Chaki, N. K.; Shichibu, Y.; Whetten, R. L.; (324) Chen, Y.; Zeng, C.; Liu, C.; Kirschbaum, K.; Gayathri, C.; Gil,
Tsukuda, T. Origin of Magic Stability of Thiolated Gold Clusters: A R. R.; Rosi, N. L.; Jin, R. Crystal Structure of Barrel-Shaped Chiral
Case Study on Au25(SC6H13)18. J. Am. Chem. Soc. 2007, 129, 11322− Au130(p-MBT)50 Nanocluster. J. Am. Chem. Soc. 2015, 137, 10076−
11323. 10079.
(306) Dass, A.; Stevenson, A.; Dubay, G. R.; Tracy, J. B.; Murray, R. (325) Dass, A.; Theivendran, S.; Nimmala, P. R.; Kumara, C.; Jupally,
W. Nanoparticle MALDI-TOF Mass Spectrometry without Fragmen- V. R.; Fortunelli, A.; Sementa, L.; Barcaro, G.; Zuo, X.; Noll, B. C.

8258 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

Au133(SPh-tBu)52 Nanomolecules: X-ray Crystallography, Optical, Molecules: Au23 vs. Au25. Phys. Chem. Chem. Phys. 2016, 18, 4822−
Electrochemical, and Theoretical Analysis. J. Am. Chem. Soc. 2015, 4827.
137, 4610−4613. (346) Kwak, K.; Lee, D. Electrochemical Characterization of Water-
(326) Gutrath, B. S.; Oppel, I. M.; Presly, O.; Beljakov, I.; Meded, V.; Soluble Au25 Nanoclusters Enabled by Phase-Transfer Reaction. J.
Wenzel, W.; Simon, U. [Au14(PPh3)8(NO3)4]: An Example of a New Phys. Chem. Lett. 2012, 3, 2476−2481.
Class of Au(NO3)-Ligated Superatom Complexes. Angew. Chem., Int. (347) Park, S.; Lee, D. Synthesis and Electrochemical and
Ed. 2013, 52, 3529−3532. Spectroscopic Characterization of Biicosahedral Au25 Clusters.
(327) Wan, X. K.; Yuan, S. F.; Lin, Z. W.; Wang, Q. M. A Chiral Gold Langmuir 2012, 28, 7049−7054.
Nanocluster Au20 Protected byTtetradentate Phosphine Ligands. (348) Kwak, K.; Kumar, S. S.; Pyo, K.; Lee, D. Ionic Liquid of a Gold
Angew. Chem., Int. Ed. 2014, 53, 2923−6. Nanocluster: A Versatile Matrix for Electrochemical Biosensors. ACS
(328) Chen, J.; Zhang, Q.-F.; Bonaccorso, T. A.; Williard, P. G.; Nano 2014, 8, 671−679.
Wang, L.-S. Controlling Gold Nanoclusters by Diphospine Ligands. J. (349) Yao, H. On the Electronic Structures of Au25(SR)18 Clusters
Am. Chem. Soc. 2014, 136, 92−95. Studied by Magnetic Circular Dichroism Spectroscopy. J. Phys. Chem.
(329) Schubert, U. Cluster-based Inorganic-Organic Hybrid Materi- Lett. 2012, 3, 1701−1706.
als. Chem. Soc. Rev. 2011, 40, 575−582. (350) Yao, H.; Iwatsu, M. Water-Soluble Phosphine-Protected Au11
(330) Pei, Y.; Gao, Y.; Zeng, X. C. Structural Prediction of Thiolate- Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in
Protected Au38: A Face-Fused Bi-icosahedral Au Core. J. Am. Chem. a Synergistic Fashion. Langmuir 2016, 32, 3284−3293.
Soc. 2008, 130, 7830−7832. (351) Jaw, H. R. C.; Mason, W. R. Magnetic Circular Dichroism
(331) Azubel, M.; Koivisto, J.; Malola, S.; Bushnell, D.; Hura, G. L.; Spectra for the octakis(triphenylphosphino)nonagold(3+) ion. Inorg.
Koh, A. L.; Tsunoyama, H.; Tsukuda, T.; Pettersson, M.; Häkkinen, Chem. 1991, 30, 275−278.
H.; Kornberg, R. D. Electron Microscopy of Gold Nanoparticles at (352) Zhu, M.; Aikens, C. M.; Hendrich, M. P.; Gupta, R.; Qian, H.;
Atomic Resolution. Science 2014, 345, 909−912. Schatz, G. C.; Jin, R. Reversible Switching of Magnetism in Thiolate-
(332) Han, Y.; He, D. S.; Liu, Y.; Xie, S.; Tsukuda, T.; Li, Z. Y. Size Protected Au25 Superatoms. J. Am. Chem. Soc. 2009, 131, 2490−2492.
and Shape of Nanoclusters: Single-Shot Imaging Approach. Small (353) Akbari-Sharbaf, A.; Hesari, M.; Workentin, M. S.; Fanchini, G.
2012, 8, 2361−2364. Electron Paramagnetic Resonance in Positively Charged Au25
(333) Parker, J. F.; Choi, J.-P.; Wang, W.; Murray, R. W. Electron Molecular Nanoclusters. J. Chem. Phys. 2013, 138, 024305.
S e l f - e x c h an g e D y n a m i c s of t h e N a n o p a r t i c l e C o u p l e (354) Ionita, P.; Volkov, A.; Jeschke, G.; Chechik, V. Lateral
[Au25(SC2Ph)18]0/1− By Nuclear Magnetic Resonance Line-Broad- Diffusion of Thiol Ligands on the Surface of Au Nanoparticles: An
ening. J. Phys. Chem. C 2008, 112, 13976−13981. Electron Paramagnetic Resonance Study. Anal. Chem. 2008, 80, 95−
(334) Wu, Z.; Jin, R. Stability of the Two Au-S Binding Modes in 106.
Au25(SG)18 Nanoclusters Probed by NMR and Optical Spectroscopy. (355) MacDonald, M. A.; Chevrier, D. M.; Zhang, P.; Qian, H.; Jin,
ACS Nano 2009, 3, 2036−2042. R. The Structure and Bonding of Au25(SR)18 Nanoclusters from
(335) Wu, Z.; Gayathri, C.; Gil, R. R.; Jin, R. Probing the Structure
EXAFS: The Interplay of Metallic and Molecular Behavior. J. Phys.
and Charge State of Glutathione-Capped Au25(SG)18 Clusters by
Chem. C 2011, 115, 15282−15287.
NMR and Mass Spectrometry. J. Am. Chem. Soc. 2009, 131, 6535−
(356) Cluskey, P. D.; Newport, R. J.; Benfield, R. E.; Gurman, S. J.;
6542.
Schmid, G. An EXAFS Study of some Gold and Palladium Cluster
(336) Stefanescu, D. M.; Glueck, D. S.; Siegel, R.; Wasylishen, R. E.
compounds. Z. Phys. D: At., Mol. Clusters 1993, 26, 8−11.
Synthesis and Characterization of Phosphido-Monolayer-Protected
(357) Shivhare, A.; Lee, K. E.; Hu, Y.; Scott, R. W. J. Following the
Gold Nanoclusters. Langmuir 2004, 20, 10379−10381.
Reactivity of Au25(SC8H9)18− Clusters with Pd2+ and Ag+ Ions Using
(337) Zhang, Q.-F.; Williard, P. G.; Wang, L.-S. Polymorphism of
in Situ X-ray Absorption Spectroscopy: A Tale of Two Metals. J. Phys.
Phosphine-Protected Gold Nanoclusters: Synthesis and Character-
ization of a New 22-Gold-Atom Cluster. Small 2016, 12, 2518−2525. Chem. C 2015, 119, 23279−23284.
(338) Clayden, N. J.; Dobson, C. M.; Hall, K. P.; Mingos, D. M. P.; (358) Zhang, P. X-ray Spectroscopy of Gold−Thiolate Nanoclusters.
Smith, D. J. Studies of Gold Cluster Compounds using High- J. Phys. Chem. C 2014, 118, 25291−25299.
resolution 31P Solid-state Nuclear Magnetic Resonance Spectroscopy. (359) Negishi, Y.; Kurashige, W.; Kobayashi, Y.; Yamazoe, S.;
J. Chem. Soc., Dalton Trans. 1985, 1811−1814. Kojima, N.; Seto, M.; Tsukuda, T. Formation of a Pd@Au12
(339) Farrag, M.; Tschurl, M.; Dass, A.; Heiz, U. Infra-red Superatomic Core in Au24Pd1(SC12H25)18 Probed by 197Au Mössbauer
Spectroscopy of Size Selected Au25, Au38 and Au144 Ligand Protected and Pd K-Edge EXAFS Spectroscopy. J. Phys. Chem. Lett. 2013, 4,
Gold Clusters. Phys. Chem. Chem. Phys. 2013, 15, 12539−42. 3579−3583.
(340) Dolamic, I.; Varnholt, B.; Burgi, T. Far-infrared Spectra of (360) Christensen, S. L.; Cho, P.; Chatt, A.; Zhang, P. A Site-specific
Well-defined Thiolate-Protected Gold Clusters. Phys. Chem. Chem. Comparative Study of Au102 and Au25 Nanoclusters Using Theoretical
Phys. 2013, 15, 19561−19565. EXAFS and l-DOS. Can. J. Chem. 2015, 93, 32−36.
(341) Varnholt, B.; Oulevey, P.; Luber, S.; Kumara, C.; Dass, A.; (361) Shivhare, A.; Chevrier, D. M.; Purves, R. W.; Scott, R. W. J.
Bürgi, T. Structural Information on the Au−S Interface of Thiolate- Following the Thermal Activation of Au25(SR)18 Clusters for Catalysis
Protected Gold Clusters: A Raman Spectroscopy Study. J. Phys. Chem. by X-ray Absorption Spectroscopy. J. Phys. Chem. C 2013, 117,
C 2014, 118, 9604−9611. 20007−20016.
(342) Liu, Z.; Xu, Q.; Jin, S.; Wang, S.; Xu, G.; Zhu, M. Electron (362) Chevrier, D. M.; Yang, R.; Chatt, A.; Zhang, P. Bonding
Transfer Reaction Between Au25 Nanocluster and Phenothiazine- Properties of Thiolate-Protected Gold Nanoclusters and Structural
tetrachloro-p-benzoquinone Complex. Int. J. Hydrogen Energy 2013, Analogs from X-ray Absorption Apectroscopy. Nanotechnol. Rev. 2015,
38, 16722−16726. 4, 193−206.
(343) Song, Y.; Fu, F.; Zhang, J.; Chai, J.; Kang, X.; Li, P.; Li, S.; (363) Bovenkamp-Langlois, L.; Schaefer, M. W. The Characterization
Zhou, H.; Zhu, M. The Magic Au60 Nanocluster: A New Cluster- of Atomically Precise Nanoclusters Using X-Ray Absorption Spec-
Assembled Material with Five Au13 Building Blocks. Angew. Chem., Int. troscopy. In X-ray and Neutron Techniques for Nanomaterials
Ed. 2015, 54, 8430−8434. Characterization; Kumar, C. S. S. R., Ed.; Springer: Berlin, 2016; pp
(344) Balasubramanian, R.; Guo, R.; Mills, A. J.; Murray, R. W. 247−313.
Reaction of Au55(PPh3)12Cl6 with Thiols Yields Thiolate Monolayer (364) Kojima, N.; Kobayashi, Y.; Negishi, Y.; Seto, M.; Tsukuda, T.
Protected Au75 Clusters. J. Am. Chem. Soc. 2005, 127, 8126−8132. Structural Evolution of Glutathionate-protected Gold Clusters Studied
(345) Matsuo, S.; Yamazoe, S.; Goh, J.-Q.; Akola, J.; Tsukuda, T. The by means of 197Au Mössbauer Spectroscopy. Hyperfine Interact. 2013,
Electrooxidation-Induced Structural Changes of Gold Di-superatomic 217, 91−98.

8259 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(365) Kojima, N.; Ikeda, K.; Kobayashi, Y.; Tsukuda, T.; Negishi, Y.; (384) Retnakumari, A.; Jayasimhan, J.; Chandran, P.; Menon, D.;
Harada, G.; Sugawara, T.; Seto, M. Study of the Structure and Nair, S.; Mony, U.; Koyakutty, M. CD33 Monoclonal Antibody
Electronic State of Thiolate-Protected Gold Clusters by means of Conjugated Au Cluster Nano-bioprobe for Targeted flow-cytometric
197
Au Mössbauer Spectroscopy. Hyperfine Interact. 2012, 207, 127− Detection of Acute Myeloid Leukaemia. Nanotechnology 2011, 22,
131. 285102.
(366) Tsukuda, T.; Negishi, Y.; Kobayashi, Y.; Kojima, N. 197Au (385) Simms, G. A.; Padmos, J. D.; Zhang, P. Structural and
Mössbauer Spectroscopy of Au25(SG)18− Revisited. Chem. Lett. 2011, Electronic Properties of Protein/thiolate-protected Gold nanocluster
40, 1292−1293. with ″Staple″ Motif: A XAS, L-DOS, and XPS study. J. Chem. Phys.
(367) Tlahuice-Flores, A. New insight into the Structure of Thiolated 2009, 131, 214703.
Gold Clusters: a Structural Prediction of the Au187(SR)68 Cluster. Phys. (386) Song, G.-B.; Xu, J.; Zheng, H.; Feng, Y.; Zhang, W.-W.; Li, K.;
Chem. Chem. Phys. 2015, 17, 5551−5555. Ge, S.-s.; Li, K.; Zhang, H. Novel Soluble Dietary Fiber-Tannin Self-
(368) Green, T. D.; Herbert, P. J.; Yi, C.; Zeng, C.; McGill, S.; Jin, R.; Assembled Film: A Promising Protein Protective Material. J. Agric.
Knappenberger, K. L. Characterization of Emissive States for Food Chem. 2015, 63, 5813−5820.
Structurally Precise Au25(SC8H9)180 Monolayer-Protected Gold Nano- (387) Song, W.; Liang, R.-P.; Wang, Y.; Zhang, L.; Qiu, J.-D. Green
clusters Using Magnetophotoluminescence Spectroscopy. J. Phys. Synthesis of Peptide-Templated Gold Nanoclusters as Novel
Chem. C 2016, 120, 17784−17790. Fluorescence Probes for Detecting Protein Kinase Activity. Chem.
(369) Yamazoe, S.; Takano, S.; Kurashige, W.; Yokoyama, T.; Nitta, Commun. 2015, 51, 10006−10009.
K.; Negishi, Y.; Tsukuda, T. Hierarchy of bond stiffnesses within (388) Su, L.; Shu, T.; Wang, J.; Zhang, Z.; Zhang, X. Hidden
icosahedral-based gold clusters protected by thiolates. Nat. Commun. Dityrosine Residues in Protein-Protected Gold Nanoclusters. J. Phys.
2016, 7, 10414. Chem. C 2015, 119, 12065−12070.
(370) Cao, X.-L.; Li, H.-W.; Yue, Y.; Wu, Y. pH-Induced (389) Su, L.; Shu, T.; Wang, Z.; Cheng, J.; Xue, F.; Li, C.; Zhang, X.
Conformational Changes of BSA in Fluorescent AuNCs at BSA and Immobilization of Bovine Serum Albumin-protected Gold Nano-
its Effects on NCs Emission. Vib. Spectrosc. 2013, 65, 186−192. clusters by using Polyelectrolytes of Opposite Charges for the
(371) Chaudhari, K.; Xavier, P. L.; Pradeep, T. Understanding the Development of the Reusable Fluorescent Cu2+-sensor. Biosens.
Evolution of Luminescent Gold Quantum Clusters in Protein Bioelectron. 2013, 44, 16−20.
Templates. ACS Nano 2011, 5, 8816−8827. (390) Tsai, C.-Y.; Li, C.-W.; Li, J.-R.; Jang, B.-H.; Chen, S.-H. Steroid
(372) Chen, S.; Zhang, J.; Jiang, S.; Lin, G.; Luo, B.; Yao, H.; Lin, Y.; Probes Conjugated with Protein-Protected Gold Nanocluster: Specific
He, C.; Liu, G.; Lin, Z. Self-Assembled Superparamagnetic Iron Oxide and Rapid Fluorescence Imaging of Steroid Receptors in Target Cells.
Nanoclusters for Universal Cell Labeling and MRI. Nanoscale Res. Lett. J. Fluoresc. 2016, 26, 1239−1248.
2016, 11, 263. (391) Zang, J.; Li, C.; Zhou, K.; Dong, H.; Chen, B.; Wang, F.; Zhao,
(373) Chen, X.; Essner, J. B.; Baker, G. A. Exploring Luminescence- G. Nanomolar Hg2+ Detection Using β-Lactoglobulin-Stabilized
based Temperature Sensing using Protein-passivated Gold Nano- Fluorescent Gold Nanoclusters in Beverage and Biological Media.
clusters. Nanoscale 2014, 6, 9594−9598.
Anal. Chem. 2016, 88, 10275−10283.
(374) Chib, R.; Butler, S.; Raut, S.; Shah, S.; Borejdo, J.; Gryczynski,
(392) Wang, L.; Hess, A.; Chang, T. Z.; Wang, Y.-C.; Champion, J.
Z.; Gryczynski, I. Effect of Quencher, Denaturants, Temperature and
A.; Compans, R. W.; Wang, B.-Z. Nanoclusters Self-assembled from
pH on the Fluorescent Properties of BSA Protected Gold Nano-
Conformation-stabilized Influenza M2e as broadly Cross-protective
clusters. J. Lumin. 2015, 168, 62−68.
Influenza Vaccines. Nanomedicine 2014, 10, 473−482.
(375) Das, T.; Maity, A.; Mondal, S.; Purkayastha, P. Modulation of
(393) Wang, L.-L.; Qiao, J.; Qi, L.; Xu, X.-Z.; Li, D. Construction of
Energy/electron Transfer in Gold Nanoclusters by Single Walled
OVA-stabilized Fluorescent Gold Nanoclusters for Sensing Glucose.
Carbon Nanotubes. Spectrochim. Acta, Part A 2015, 141, 144−148.
(376) Gerdon, A. E.; Wright, D. W.; Cliffel, D. E. Quartz Crystal Sci. China: Chem. 2015, 58, 1508−1514.
Microbalance Detection of Glutathione-Protected Nanoclusters using (394) Wang, Y.; Wang, Y.; Zhou, F.; Kim, P.; Xia, Y. Protein-
Antibody Recognition. Anal. Chem. 2005, 77, 304−310. Protected Au Clusters as a New Class of Nanoscale Biosensor for
(377) Gerdon, A. E.; Wright, D. W.; Cliffel, D. E. Epitope Mapping Label-Free Fluorescence Detection of Proteases. Small 2012, 8, 3769−
of the Protective Antigen of B. anthracis by using Nanoclusters 3773.
Presenting Conformational Peptide Epitopes. Angew. Chem., Int. Ed. (395) Xu, S.; Lu, X.; Yao, C.; Huang, F.; Jiang, H.; Hua, W.; Na, N.;
2006, 45, 594−598. Liu, H.; Ouyang, J. A Visual Sensor Array for Pattern Recognition
(378) Li, H.; Guo, Y.; Xiao, L.; Chen, B. Selective and Sensitive Analysis of Proteins Using Novel Blue-Emitting Fluorescent Gold
Detection of acetylcholinesterase Activity using Denatured Protein- Nanoclusters. Anal. Chem. 2014, 86, 11634−11639.
protected Gold Nanoclusters as a label-free probe. Analyst 2014, 139, (396) Yan, L.; Cai, Y.; Zheng, B.; Yuan, H.; Guo, Y.; Xiao, D.; Choi,
285−289. M. M. F. Microwave-assisted Synthesis of BSA-Stabilized and HSA-
(379) Liu, X.; Fu, C.; Ren, X.; Liu, H.; Li, L.; Meng, X. Fluorescence Protected Gold Nanoclusters with Red emission. J. Mater. Chem. 2012,
Switching Method for Cascade detection of Salicylaldehyde and 22, 1000−1005.
Zinc(II) ion using Protein Protected Gold Nanoclusters. Biosens. (397) Yoshimoto, J.; Sangsuwan, A.; Osaka, I.; Yamashita, K.;
Bioelectron. 2015, 74, 322−328. Iwasaki, Y.; Inada, M.; Arakawa, R.; Kawasaki, H. Optical Properties of
(380) Loftus, A. F.; Reighard, K. P.; Kapourales, S. A.; Leopold, M. C. 2-Methacryloyloxyethyl Phosphorylcholine-Protected Au4 Nanoclus-
Monolayer-Protected Nanoparticle Film Assemblies as Platforms for ters and Their Fluorescence Sensing of C-Reactive Protein. J. Phys.
Controlling Interfacial and Adsorption Properties in Protein Chem. C 2015, 119, 14319−14325.
Monolayer Electrochemistry. J. Am. Chem. Soc. 2008, 130, 1649−1661. (398) Yue, Y.; Li, H.-W.; Liu, T.-Y.; Wu, Y. Exploring the role of
(381) Mitra, A.; Bhaumik, A. Nanoscale Silver Cluster Embedded in Ligand-BSA in the Response of BSA-protected Gold-nanoclusters to
Artificial Heterogeneous Matrix Consisting of Protein and Sodium Silver (I) Ions by FT-IR and Circular dichroism Spectra. Vib. Spectrosc.
Polyacrylate. Mater. Lett. 2007, 61, 659−662. 2014, 74, 137−141.
(382) Raut, S.Development of Novel Fluorescent Probe- Protein Protected (399) Zhang, M.; Dang, Y.-Q.; Liu, T.-Y.; Li, H.-W.; Wu, Y.; Li, Q.;
Gold Nanoclusters for Biomedical Applications. Ph.D. Thesis, University Wang, K.; Zou, B. Pressure-Induced Fluorescence Enhancement of the
of North Texas Health Science Center at Fort Worth, 2013; 122 pp. BSA-Protected Gold Nanoclusters and the Corresponding Conforma-
(383) Raut, S.; Chib, R.; Butler, S.; Borejdo, J.; Gryczynski, Z.; tional Changes of Protein. J. Phys. Chem. C 2013, 117, 639−647.
Gryczynski, I. Evidence of energy transfer from tryptophan to BSA/ (400) Zhang, X.-D.; Luo, Z.; Chen, J.; Song, S.; Yuan, X.; Shen, X.;
HSA protected gold nanoclusters. Methods Appl. Fluoresc. 2014, 2, Wang, H.; Sun, Y.; Gao, K.; Zhang, L.; Fan, S.; Leong, D. T.; Guo, M.;
035004. Xie, J. Ultrasmall Glutathione-Protected Gold Nanoclusters as Next

8260 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

Generation Radiotherapy Sensitizers with High Tumor Uptake and (421) Sugiuchi, M.; Shichibu, Y.; Nakanishi, T.; Hasegawa, Y.;
High Renal Clearance. Sci. Rep. 2015, 5, 8669. Konishi, K. Cluster-[small pi] Electronic Interaction in a Superatomic
(401) Baksi, A.; Xavier, P. L.; Chaudhari, K.; Goswami, N.; Pal, S. K.; Au13 Cluster Bearing [sigma]-bonded Acetylide Ligands. Chem.
Pradeep, T. Protein-Encapsulated Gold Cluster Aggregates: the Case Commun. 2015, 51, 13519−13522.
of Lysozyme. Nanoscale 2013, 5, 2009−2016. (422) Antoku, Y.; Hotta, J.-I.; Mizuno, H.; Dickson, R. M.; Hofkens,
(402) Mukhopadhyay, R.; Mitra, S.; Johnson, M.; Rajeev Kumar, V. J.; Vosch, T. Transfection of Living HeLa Cells with Fluorescent Poly-
R.; Pradeep, T. Evolution of the Alkyl-chain Dynamics in Monolayer- cytosine Encapsulated Ag Nanoclusters. Photochem. Photobiol. Sci.
protected Gold Clusters. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 9, 716−721.
2007, 75, 075414. (423) Peyser-Capadona, L.; Zheng, J.; Gonzalez, J. I.; Lee, T.-H.;
(403) Resmi, M. R.; Sandhyarani, N.; Unnikrishnan, R.; Ma, S.; Patel, S. A.; Dickson, R. M. Nanoparticle-free single molecule anti-
Pradeep, T. Charge-Transfer Complexation of C60 with Diphenylte- Stokes Raman spectroscopy. Phys. Rev. Lett. 2005, 94, 058301.
trathiafulvalene (DPTTF) Capped Gold Clusters. J. Colloid Interface (424) Choi, S.; Dickson, R. M.; Yu, J. Developing Luminescent Silver
Sci. 1999, 217, 395−402. Nanodots for Biological Applications. Chem. Soc. Rev. 2012, 41, 1867−
(404) Gautier, C.; Taras, R.; Gladiali, S.; Burgi, T. Chiral 1,1′- 1891.
binaphthyl-2,2′-dithiol-Stabilized Gold Clusters: Size Separation and (425) Choi, S.; Yu, J.; Patel, S. A.; Tzeng, Y.-L.; Dickson, R. M.
Optical Activity in the UV-vis. Chirality 2008, 20, 486−493. Tailoring Silver Nanodots for Intracellular Staining. Photochem.
(405) Wolfe, R. L.; Balasubramanian, R.; Tracy, J. B.; Murray, R. W. Photobiol. Sci. 2011, 10, 109−115.
Fully Ferrocenated Hexanethiolate Monolayer-Protected Gold Clus- (426) Dickson, R. M.; Lee, T.-H. Harnessing Ag Nanocluster
ters. Langmuir 2007, 23, 2247−2254. Dynamics for Nanotechnology. Presented at the National Meeting of
(406) Kurashige, W.; Yamaguchi, M.; Nobusada, K.; Negishi, Y. the American Chemical Society, 2003; Paper PHYS 238.
Ligand-Induced Stability of Gold Nanoclusters: Thiolate versus (427) Dickson, R. M.; Lyon, L. A. Apparatus and Method of Optical
Selenolate. J. Phys. Chem. Lett. 2012, 3, 2649−2652. Transfer and Control in Plasmon Supporting Metal Nanostructures.
(407) Negishi, Y.; Arai, R.; Niihori, Y.; Tsukuda, T. Isolation and U.S. Patent US6539156B1, 2003.
Structural Characterization of Magic Silver Clusters Protected by 4- (428) Lee, T.-H.; Dickson, R. M. Single-Molecule LEDs from
(tert-butyl)benzyl Mercaptan. Chem. Commun. 2011, 47, 5693−5695. Nanoscale Electroluminescent Junctions. J. Phys. Chem. B 2003, 107,
(408) Kurashige, W.; Yamazoe, S.; Kanehira, K.; Tsukuda, T.; 7387−7390.
Negishi, Y. Selenolate-Protected Au38 Nanoclusters: Isolation and (429) Lee, T.-H.; Dickson, R. M. Nanocomputing with Nanoclusters.
Structural Characterization. J. Phys. Chem. Lett. 2013, 4, 3181−3185. Opt. Photonics News 2004, 15, 22−27.
(409) Kurashige, W.; Yamazoe, S.; Yamaguchi, M.; Nishido, K.; (430) Lee, T.-H.; Gonzalez, J. I.; Dickson, R. M. Strongly Enhanced
Nobusada, K.; Tsukuda, T.; Negishi, Y. Au25 Clusters Containing field-dependent Single-Molecule Electroluminescence. Proc. Natl.
Unoxidized Tellurolates in the Ligand Shell. J. Phys. Chem. Lett. 2014, Acad. Sci. U. S. A. 2002, 99, 10272−5.
5, 2072−2076. (431) Lee, T.-H.; Gonzalez, J. I.; Zheng, J.; Dickson, R. M. Single-
(410) Kawasaki, H.; Yamamoto, H.; Fujimori, H.; Arakawa, R.; Molecule Optoelectronics. Acc. Chem. Res. 2005, 38, 534−541.
Iwasaki, Y.; Inada, M. Stability of the DMF-Protected Au Nano- (432) Patel, S. A.; Cozzuol, M.; Hales, J. M.; Richards, C. I.; Sartin,
clusters: Photochemical, Dispersion, and Thermal Properties. M.; Hsiang, J.-C.; Vosch, T.; Perry, J. W.; Dickson, R. M. Electron
Langmuir 2010, 26, 5926−5933. Transfer-Induced Blinking in Ag Nanodot Fluorescence. J. Phys. Chem.
(411) Schmid, G.; Beyer, N. A New Approach to Well-Ordered C 2009, 113, 20264−20270.
Quantum Dots. Eur. J. Inorg. Chem. 2000, 2000, 835−837. (433) Patel, S. A.; Richards, C. I.; Hsiang, J.-C.; Dickson, R. M.
(412) Schmid, G.; Meyer-Zaika, W.; Pugin, R.; Sawitowski, T.; Water-Soluble Ag Nanoclusters Exhibit Strong Two-Photon-Induced
Majoral, J.-P.; Caminade, A.-M.; Turrin, C.-O. Naked Au55 Clusters: Fluorescence. J. Am. Chem. Soc. 2008, 130, 11602−11603.
Dramatic Effect of a Thiol-Terminated Dendrimer. Chem. - Eur. J. (434) Petty, J. T.; Fan, C.; Story, S. P.; Sengupta, B.; St. John Iyer, A.;
2000, 6, 1693−1697. Prudowsky, Z.; Dickson, R. M. DNA Encapsulation of 10 Silver Atoms
(413) Schmid, G. n.; Liu, Y.-P.; Schumann, M.; Raschke, T.; Producing a Bright, Modulatable, Near-Infrared-Emitting Cluster. J.
Radehaus, C. Quasi One-Dimensional Arrangements of Phys. Chem. Lett. 2010, 1, 2524−2529.
Au55(PPh3)12Cl6 Clusters and Their Electrical Properties at Room (435) Petty, J. T.; Fan, C.-Y.; Story, S. P.; Sengupta, B.; Sartin, M.;
Temperature. Nano Lett. 2001, 1, 405−407. Hsiang, J.-C.; Perry, J. W.; Dickson, R. M. Optically Enhanced, Near-
(414) Tsunoyama, H.; Ichikuni, N.; Sakurai, H.; Tsukuda, T. Effect of IR, Silver Cluster Emission Altered by Single Base Changes in the
Electronic Structures of Au Clusters Stabilized by Poly(N-vinyl-2- DNA Template. J. Phys. Chem. B 2011, 115, 7996−8003.
pyrrolidone) on Aerobic Oxidation Catalysis. J. Am. Chem. Soc. 2009, (436) Petty, J. T.; Story, S. P.; Hsiang, J.-C.; Dickson, R. M. DNA-
131, 7086−7093. Templated Molecular Silver Fluorophores. J. Phys. Chem. Lett. 2013, 4,
(415) Tsunoyama, H.; Ichikuni, N.; Tsukuda, T. Microfluidic 1148−1155.
Synthesis and Catalytic Application of PVP-Stabilized, ∼ 1 nm Gold (437) Petty, J. T.; Zheng, J.; Hud, N. V.; Dickson, R. M. DNA-
Clusters. Langmuir 2008, 24, 11327−11330. templated Ag Nanocluster formation. J. Am. Chem. Soc. 2004, 126,
(416) Tsunoyama, H.; Sakurai, H.; Negishi, Y.; Tsukuda, T. Size- 5207−5212.
Specific Catalytic Activity of Polymer-Stabilized Gold Nanoclusters for (438) Peyser, L. A.; Vinson, A. E.; Bartko, A. P.; Dickson, R. M.
Aerobic Alcohol Oxidation in Water. J. Am. Chem. Soc. 2005, 127, Photoactivated Fluorescence from Individual Silver Nanoclusters.
9374−9375. Science 2001, 291, 103−106.
(417) Tsunoyama, H.; Tsukuda, T. Magic Numbers of Gold Clusters (439) Richards, C. I.; Choi, S.; Hsiang, J.-C.; Antoku, Y.; Vosch, T.;
Stabilized by PVP. J. Am. Chem. Soc. 2009, 131, 18216−18217. Bongiorno, A.; Tzeng, Y.-L.; Dickson, R. M. Oligonucleotide-Stabilized
(418) Maity, P.; Takano, S.; Yamazoe, S.; Wakabayashi, T.; Tsukuda, Ag Nanocluster Fluorophores. J. Am. Chem. Soc. 2008, 130, 5038−
T. Binding Motif of Terminal Alkynes on Gold Clusters. J. Am. Chem. 5039.
Soc. 2013, 135, 9450−9457. (440) Richards, C. I.; Hsiang, J.-C.; Senapati, D.; Patel, S.; Yu, J.;
(419) Maity, P.; Tsunoyama, H.; Yamauchi, M.; Xie, S.; Tsukuda, T. Vosch, T.; Dickson, R. M. Optically Modulated Fluorophores for
Organogold Clusters Protected by Phenylacetylene. J. Am. Chem. Soc. Selective Fluorescence Signal Recovery. J. Am. Chem. Soc. 2009, 131,
2011, 133, 20123−20125. 4619−4621.
(420) Maity, P.; Wakabayashi, T.; Ichikuni, N.; Tsunoyama, H.; Xie, (441) Ritchie, C. M.; Johnsen, K. R.; Kiser, J. R.; Antoku, Y.;
S.; Yamauchi, M.; Tsukuda, T. Selective Synthesis of Organogold Dickson, R. M.; Petty, J. T. Ag Nanocluster formation using a Cytosine
Magic Clusters Au54(CCPh)26. Chem. Commun. 2012, 48, 6085−6087. Oligonucleotide Template. J. Phys. Chem. C 2007, 111, 175−181.

8261 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(442) Vosch, T.; Antoku, Y.; Hsiang, J.-C.; Richards, C. I.; Gonzalez, Properties of a Large Box-Shaped Silver Nanocluster. J. Am. Chem. Soc.
J. I.; Dickson, R. M. Strongly Emissive Individual DNA-encapsulated 2016, 138, 14727−14732.
Ag Nanoclusters as Single-molecule fluorophores. Proc. Natl. Acad. Sci. (460) Yang, H.; Wang, Y.; Chen, X.; Zhao, X.; Gu, L.; Huang, H.;
U. S. A. 2007, 104, 12616−12621. Yan, J.; Xu, C.; Li, G.; Wu, J.; Edwards, A. J.; Dittrich, B.; Tang, Z.;
(443) Yu, J.; Choi, S.; Dickson, R. M. Shuttle-based Fluorogenic Wang, D.; Lehtovaara, L.; Hakkinen, H.; Zheng, N. Plasmonic
Silver-cluster Biolabels. Angew. Chem., Int. Ed. 2009, 48, 318−320. Twinned Silver Nanoparticles with Molecular Precision. Nat. Commun.
(444) Yu, J.; Choi, S.; Richards, C. I.; Antoku, Y.; Dickson, R. M. Live 2016, 7, 12809.
Cell Surface Labeling with Fluorescent Ag Nanocluster Conjugates. (461) Remya, K. P.; Udayabhaskararao, T.; Pradeep, T. Low-
Photochem. Photobiol. 2008, 84, 1435−1439. Temperature Thermal Dissociation of Ag Quantum Clusters in
(445) Yu, J.; Patel, S. A.; Dickson, R. M. In vitro and Intracellular Solution and Formation of Monodisperse Ag2S Nanoparticles. J. Phys.
Production of Peptide-Encapsulated Fluorescent Silver Nanoclusters. Chem. C 2012, 116, 26019−26026.
Angew. Chem., Int. Ed. 2007, 46, 2028−2030. (462) Delamarche, E.; Michel, B.; Kang, H.; Gerber, C. Thermal
(446) Zheng, J.; Capadona, L. A.; Petty, J. T.; Zhang, C.; Tzeng, Y.- Stability of Self-Assembled Monolayers. Langmuir 1994, 10, 4103−
L.; Dickson, R. M. Highly Fluorescent, Size-tunable, Water-soluble Au 4108.
and Ag Nanodots for Single Molecule Biophysics in Living Systems. (463) Terrill, R. H.; Postlethwaite, T. A.; Chen, C.-h.; Poon, C.-D.;
Presented at the National Meeting of the American Chemical Society, Terzis, A.; Chen, A.; Hutchison, J. E.; Clark, M. R.; Wignall, G.
2004; Paper PHYS-072. Monolayers in Three Dimensions: NMR, SAXS, Thermal, and
(447) Zheng, J.; Dickson, R. M. Individual Water-Soluble Dendrimer- Electron Hopping Studies of Alkanethiol Stabilized Gold Clusters. J.
Encapsulated Silver Nanodot Fluorescence. J. Am. Chem. Soc. 2002, Am. Chem. Soc. 1995, 117, 12537−12548.
124, 13982−13983. (464) Nuzzo, R.; Korenic, E.; Dubois, L. Studies of the Temperature-
(448) Cathcart, N.; Kitaev, V. Silver Nanoclusters: Single-Stage Dependent Phase Behavior of Long Chain n-alkyl Thiol Monolayers
Scaleable Synthesis of Monodisperse Species and Their Chirooptical on Gold. J. Chem. Phys. 1990, 93, 767−773.
Properties. J. Phys. Chem. C 2010, 114, 16010−16017. (465) Buttner, M.; Belser, T.; Oelhafen, P. Stability of Thiol-
(449) AbdulHalim, L. G.; Hooshmand, Z.; Parida, M. R.; Aly, S. M.; passivated Gold Particles at Elevated Temperatures Studied by X-ray
Le, D.; Zhang, X.; Rahman, T. S.; Pelton, M.; Losovyj, Y.; Dowben, P. Photoelectron Spectroscopy. J. Phys. Chem. B 2005, 109, 5464−5467.
A.; Bakr, O. M.; Mohammed, O. F.; Katsiev, K. pH-Induced Surface (466) Murty, K. V. G. K.; Venkataramanan, M.; Pradeep, T. Self-
Modification of Atomically Precise Silver Nanoclusters: An Approach assembled Monolayers of 1,4-Benzenedimethanethiol on Polycrystal-
for Tunable Optical and Electronic Properties. Inorg. Chem. 2016, 55,
line Silver and Gold Films: An Investigation of Structure, Stability,
11522−11528.
Dynamics, and Reactivity. Langmuir 1998, 14, 5446−5456.
(450) Bakr, O. M.; Amendola, V.; Aikens, C. M.; Wenseleers, W.; Li,
(467) Mie, G. Beiträge zur Optik trüber Medien, speziell kolloidaler
R.; Dal Negro, L.; Schatz, G. C.; Stellacci, F. Silver Nanoparticles with
Metallösungen. Ann. Phys. 1908, 330, 377−445.
Broad Multiband Linear Optical Absorption. Angew. Chem. 2009, 121,
(468) Sugi, K. S.; Chakraborty, I.; Udayabhaskararao, T.; Mohanty, J.
6035−6040.
S.; Pradeep, T. Evolution of Atomically Precise Silver Clusters to
(451) Cathcart, N.; Mistry, P.; Makra, C.; Pietrobon, B.; Coombs, N.;
Superlattice Crystals. Part. Part. Sys. Charact. 2013, 30, 241−243.
Jelokhani-Niaraki, M.; Kitaev, V. Chiral Thiol-Stabilized Silver
(469) Taylor, K. J.; Pettiette-Hall, C. L.; Cheshnovsky, O.; Smalley,
Nanoclusters with Well-Resolved Optical Transitions Synthesized by
R. E. Ultraviolet Photoelectron Spectra of Coinage Metal Clusters. J.
a Facile Etching Procedure in Aqueous Solutions. Langmuir 2009, 25,
Chem. Phys. 1992, 96, 3319−3329.
5840−5846.
(470) Si, S.; Gautier, C.; Boudon, J.; Taras, R.; Gladiali, S.; Bürgi, T.
(452) Díez, I.; Pusa, M.; Kulmala, S.; Jiang, H.; Walther, A.;
Goldmann, A. S.; Müller, A. H. E.; Ikkala, O.; Ras, R. H. A. Color Ligand Exchange on Au25 Cluster with Chiral Thiols. J. Phys. Chem. C
Tunability and Electrochemiluminescence of Silver Nanoclusters. 2009, 113, 12966−12969.
Angew. Chem., Int. Ed. 2009, 48, 2122−2125. (471) Reyes, E. n.; Madueño, R.; Blázquez, M.; Pineda, T. Facile
(453) Nishida, N.; Yao, H.; Kimura, K. Chiral Functionalization of Exchange of Ligands on the 6-Mercaptopurine-Monolayer Protected
Optically Inactive Monolayer-Protected Silver Nanoclusters by Chiral Gold Clusters Surface. J. Phys. Chem. C 2010, 114, 15955−15962.
Ligand-Exchange Reactions. Langmuir 2008, 24, 2759−2766. (472) Knoppe, S.; Dharmaratne, A. C.; Schreiner, E.; Dass, A.; Bürgi,
(454) Ritchie, C. M.; Johnsen, K. R.; Kiser, J. R.; Antoku, Y.; T. Ligand Exchange Reactions on Au38 and Au40 Clusters: A
Dickson, R. M.; Petty, J. T. Ag Nanocluster Formation Using a Combined Circular Dichroism and Mass Spectrometry Study. J. Am.
Cytosine Oligonucleotide Template. J. Phys. Chem. C 2007, 111, 175− Chem. Soc. 2010, 132, 16783−16789.
181. (473) Grant, C. D.; Schwartzberg, A. M.; Yang, Y.; Chen, S.; Zhang,
(455) Wu, Z.; Lanni, E.; Chen, W.; Bier, M. E.; Ly, D.; Jin, R. High J. Z. Ultrafast Study of Electronic Relaxation Dynamics in Au11
Yield, Large Scale Synthesis of Thiolate-Protected Ag7 Clusters. J. Am. Nanoclusters. Chem. Phys. Lett. 2004, 383, 31−34.
Chem. Soc. 2009, 131, 16672−16674. (474) Woehrle, G. H.; Warner, M. G.; Hutchison, J. E. Ligand
(456) Zheng, K.; Yuan, X.; Kuah, K.; Luo, Z.; Yao, Q.; Zhang, Q.; Exchange Reactions Yield Subnanometer, Thiol-Stabilized Gold
Xie, J. Boiling Water Synthesis of Ultrastable Thiolated Silver Particles with Defined Optical Transitions. J. Phys. Chem. B 2002,
Nanoclusters with Aggregation-induced Emission. Chem. Commun. 106, 9979−9981.
2015, 51, 15165−15168. (475) Habeeb Muhammed, M.; Ramesh, S.; Sinha, S.; Pal, S.;
(457) AbdulHalim, L. G.; Bootharaju, M. S.; Tang, Q.; Del Gobbo, Pradeep, T. Two Distinct Fluorescent Quantum Clusters of Gold
S.; AbdulHalim, R. G.; Eddaoudi, M.; Jiang, D.-e.; Bakr, O. M. Starting from Metallic Nanoparticles by pH-dependent Ligand
Ag29(BDT)12(TPP)4: A Tetravalent Nanocluster. J. Am. Chem. Soc. Etching. Nano Res. 2008, 1, 333−340.
2015, 137, 11970−11975. (476) Habeeb Muhammed, M. A.; Pradeep, T. Aqueous to Organic
(458) Baksi, A.; Harvey, S. R.; Natarajan, G.; Wysocki, V. H.; Phase Transfer of Au25 Clusters. J. Cluster Sci. 2009, 20, 365−373.
Pradeep, T. Possible Isomers in Ligand Protected Ag11 Cluster Ions (477) Shichibu, Y.; Negishi, Y.; Tsukuda, T.; Teranishi, T. Large-
Identified by Ion Mobility Mass Spectrometry and Fragmented by Scale Synthesis of Thiolated Au25 Clusters via Ligand Exchange
Surface Induced Dissociation. Chem. Commun. 2016, 52, 3805−3808. Reactions of Phosphine-Stabilized Au11 Clusters. J. Am. Chem. Soc.
(459) Alhilaly, M. J.; Bootharaju, M. S.; Joshi, C. P.; Besong, T. M. 2005, 127, 13464−13465.
D.; Emwas, A.-H.; Juarez Mosqueda, R.; Kaappa, S.; Malola, S.; Adil, (478) Muhammed, M. A. H.; Shaw, A. K.; Pal, S. K.; Pradeep, T.
K.; Shkurenko, A.; Häkkinen, H.; Eddaoudi, M.; Bakr, O. M. Quantum Clusters of Gold Exhibiting FRET. J. Phys. Chem. C 2008,
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical 112, 14324−14330.

8262 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(479) Zhang, B.; Salassa, G.; Burgi, T. Silver Migration between (498) Zeng, J.-L.; Guan, Z.-J.; Du, Y.; Nan, Z.-A.; Lin, Y.-M.; Wang,
Au38(SC2H4Ph)24 and Doped AgxAu38‑x(SC2H4Ph)24 Nanoclusters. Q.-M. Chloride-Promoted Formation of a Bimetallic Nanocluster
Chem. Commun. 2016, 52, 9205−9207. Au80Ag30 and the Total Structure Determination. J. Am. Chem. Soc.
(480) Baksi, A.; Chakraborty, P.; Bhat, S.; Natarajan, G.; Pradeep, T. 2016, 138, 7848−7851.
[Au25(SR)18]22−: A Noble Metal Cluster Dimer in the Gas Phase. (499) Christensen, S. L.; MacDonald, M. A.; Chatt, A.; Zhang, P.;
Chem. Commun. 2016, 52, 8397−8400. Qian, H.; Jin, R. Dopant Location, Local Structure, and Electronic
(481) Smith, J. G.; Chakraborty, I.; Jain, P. K. In Situ Single- Properties of Au24Pt(SR)18 Nanoclusters. J. Phys. Chem. C 2012, 116,
Nanoparticle Spectroscopy Study of Bimetallic Nanostructure 26932−26937.
Formation. Angew. Chem., Int. Ed. 2016, 55, 9979−9983. (500) Yao, C.; Chen, J.; Li, M.-B.; Liu, L.; Yang, J.; Wu, Z. Adding
(482) Jin, R.; Zhao, S.; Xing, Y.; Jin, R. All-thiolate-protected Silver Two Active Silver Atoms on Au25 Nanoparticle. Nano Lett. 2015, 15,
and Silver-rich Alloy Nanoclusters with Atomic Precision: Stable Sizes, 1281−1287.
Structural Characterization and Optical Properties. CrystEngComm (501) Wang, Y.; Su, H.; Xu, C.; Li, G.; Gell, L.; Lin, S.; Tang, Z.;
2016, 18, 3996−4005. Häkkinen, H.; Zheng, N. An Intermetallic Au24Ag20 Superatom
(483) Bruma, A.; Negreiros, F. R.; Xie, S.; Tsukuda, T.; Johnston, R. Nanocluster Stabilized by Labile Ligands. J. Am. Chem. Soc. 2015, 137,
L.; Fortunelli, A.; Li, Z. Y. Direct Atomic Imaging and Density 4324−4327.
Functional Theory Study of the Au24Pd1 Cluster Catalyst. Nanoscale (502) Wang, S.; Song, Y.; Jin, S.; Liu, X.; Zhang, J.; Pei, Y.; Meng, X.;
2013, 5, 9620−9625. Chen, M.; Li, P.; Zhu, M. Metal Exchange Method Using Au25
(484) Tofanelli, M. A.; Ni, T. W.; Phillips, B. D.; Ackerson, C. J. Nanoclusters as Templates for Alloy Nanoclusters with Atomic
Crystal Structure of the PdAu24(SR)180 Superatom. Inorg. Chem. 2016, Precision. J. Am. Chem. Soc. 2015, 137, 4018−4021.
55, 999−1001. (503) Wen, X.; Yu, P.; Toh, Y.-R.; Tang, J. Structure-Correlated Dual
(485) Negishi, Y.; Iwai, T.; Ide, M. Continuous Modulation of Fluorescent Bands in BSA-Protected Au25 Nanoclusters. J. Phys. Chem.
Electronic Structure of Stable Thiolate-protected Au25 Cluster by Ag C 2012, 116, 11830−11836.
doping. Chem. Commun. 2010, 46, 4713−4715. (504) Yue, Y.; Liu, T.-Y.; Li, H.-W.; Liu, Z.; Wu, Y. Microwave-
(486) Yamazoe, S.; Kurashige, W.; Nobusada, K.; Negishi, Y.; assisted Synthesis of BSA-Protected Small Gold Nanoclusters and their
Tsukuda, T. Preferential Location of Coinage Metal Dopants (M = Ag Fluorescence-enhanced Sensing of silver(i) ions. Nanoscale 2012, 4,
or Cu) in [Au25−xMx(SC2H4Ph)18]− (x ∼ 1) As Determined by 2251−2254.
Extended X-ray Absorption Fine Structure and Density Functional (505) Zhou, W.; Cao, Y.; Sui, D.; Guan, W.; Lu, C.; Xie, J. Ultrastable
Theory Calculations. J. Phys. Chem. C 2014, 118, 25284−25290. BSA-capped Gold Nanoclusters with a Polymer-like Shielding Layer
(487) Yang, S.; Wang, S.; Jin, S.; Chen, S.; Sheng, H.; Zhu, M. A Against Reactive Oxygen Species in Living Cells. Nanoscale 2016, 8,
metal Exchange Method for Thiolate-protected Tri-metal 9614−9620.
M1AgxAu24‑x(SR)180 (M = Cd/Hg) Nanoclusters. Nanoscale 2015, 7, (506) Mohanty, J. S.; Baksi, A.; Lee, H.; Pradeep, T. Noble Metal
10005−10007. Clusters Protected with Mixed Proteins Exhibit Intense Photo-
(488) Yang, H.; Wang, Y.; Lei, J.; Shi, L.; Wu, X.; Mäkinen, V.; Lin, luminescence. RSC Adv. 2015, 5, 48039−48045.
S.; Tang, Z.; He, J.; Häkkinen, H.; Zheng, L.; Zheng, N. Ligand- (507) Habeeb Muhammed, M. A.; Verma, P. K.; Pal, S. K.;
Stabilized Au13Cux (x = 2, 4, 8) Bimetallic Nanoclusters: Ligand Retnakumari, A.; Koyakutty, M.; Nair, S.; Pradeep, T. Luminescent
Engineering to Control the Exposure of Metal Sites. J. Am. Chem. Soc. Quantum Clusters of Gold in Bulk by Albumin-Induced Core Etching
2013, 135, 9568−9571. of Nanoparticles: Metal Ion Sensing, Metal-Enhanced Luminescence,
(489) Yan, J.; Su, H.; Yang, H.; Malola, S.; Lin, S.; Häkkinen, H.; and Biolabeling. Chem. - Eur. J. 2010, 16, 10103−10112.
Zheng, N. Total Structure and Electronic Structure Analysis of Doped (508) Le Guével, X.; Hötzer, B.; Jung, G.; Hollemeyer, K.; Trouillet,
Thiolated Silver [MAg24(SR)18]2− (M = Pd, Pt) Clusters. J. Am. Chem. V.; Schneider, M. Formation of Fluorescent Metal (Au, Ag)
Soc. 2015, 137, 11880−11883. Nanoclusters Capped in Bovine Serum Albumin Followed by
(490) Wang, S.; Jin, S.; Yang, S.; Chen, S.; Song, Y.; Zhang, J.; Zhu, Fluorescence and Spectroscopy. J. Phys. Chem. C 2011, 115, 10955−
M. Total Structure Determination of Surface Doping 10963.
[Ag46Au24(SR)32](BPh4)2 Nanocluster and its Structure-Related (509) Mohanty, J. S.; Xavier, P. L.; Chaudhari, K.; Bootharaju, M.;
Catalytic Property. Sci. Adv. 2015, 1, e1500441. Goswami, N.; Pal, S.; Pradeep, T. Luminescent, Bimetallic AuAg Alloy
(491) Yan, N.; Liao, L.; Yuan, J.; Lin, Y.-J.; Weng, L.-H.; Yang, J.; Wu, Quantum Clusters in Protein Templates. Nanoscale 2012, 4, 4255−
Z. Bi-metal Doping in Nanoclusters: Synergistic or Counteractive? 4262.
Chem. Mater. 2016, 28, 8240−8247. (510) Wei, H.; Wang, Z.; Yang, L.; Tian, S.; Hou, C.; Lu, Y.
(492) Qian, H.; Barry, E.; Zhu, Y.; Jin, R. Doping 25-Atom and 38- Lysozyme-stabilized Gold Fluorescent Cluster: Synthesis and
Atom Gold Nanoclusters with Palladium. Acta Phys.-Chim. Sin. 2011, Application as Hg2+ sensor. Analyst 2010, 135, 1406−1410.
27, 513−519. (511) Lin, Y.-H.; Tseng, W.-L. Ultrasensitive Sensing of Hg2+ and
(493) Negishi, Y.; Igarashi, K.; Munakata, K.; Ohgake, W.; Nobusada, CH3Hg+ Based on the Fluorescence Quenching of Lysozyme Type VI-
K. Palladium Doping of Magic Gold Cluster Au38(SC2H4Ph)24: Stabilized Gold Nanoclusters. Anal. Chem. 2010, 82, 9194−9200.
Formation of Pd2Au36(SC2H4Ph)24 with Higher Stability than (512) Chen, W. Y.; Lin, J.-Y.; Chen, W.-J.; Luo, L.; Wei-Guang Diau,
Au38(SC2H4Ph)24. Chem. Commun. 2012, 48, 660−662. E.; Chen, Y.-C. Functional Gold Nanoclusters as Antimicrobial Agents
(494) Kumara, C.; Dass, A. (AuAg)144(SR)60 Alloy Nanomolecules. for Antibiotic-resistant Aacteria. Nanomedicine 2010, 5, 755−764.
Nanoscale 2011, 3, 3064−3067. (513) Sreeprasad, T. S.; Maliyekkal, M. S.; Deepti, K.; Chaudhari, K.;
(495) Biltek, S. R.; Mandal, S.; Sen, A.; Reber, A. C.; Pedicini, A. F.; Xavier, P. L.; Pradeep, T. Transparent, Luminescent, Antibacterial and
Khanna, S. N. Synthesis and Structural Characterization of an Atom- Patternable Film Forming Composites of Graphene Oxide/Reduced
Precise Bimetallic Nanocluster, Ag4Ni2(DMSA)4. J. Am. Chem. Soc. Graphene Oxide. ACS Appl. Mater. Interfaces 2011, 3, 2643−2654.
2013, 135, 26−29. (514) Liu, C.-L.; Wu, H.-T.; Hsiao, Y.-H.; Lai, C.-W.; Shih, C.-W.;
(496) Yan, J.; Su, H.; Yang, H.; Hu, C.; Malola, S.; Lin, S.; Teo, B. K.; Peng, Y.-K.; Tang, K.-C.; Chang, H.-W.; Chien, Y.-C.; Hsiao, J.-K.;
Häkkinen, H.; Zheng, N. Asymmetric Synthesis of Chiral Bimetallic Cheng, J.-T.; Chou, P.-T. Insulin-Directed Synthesis of Fluorescent
[Ag28Cu12(SR)24]4− Nanoclusters via Ion Pairing. J. Am. Chem. Soc. Gold Nanoclusters: Preservation of Insulin Bioactivity and Versatility
2016, 138, 12751−12754. in Cell Imaging. Angew. Chem. 2011, 123, 7194−7198.
(497) Bootharaju, M. S.; Sinatra, L.; Bakr, O. M. Distinct Metal- (515) Garcia, A. R.; Rahn, I.; Johnson, S.; Patel, R.; Guo, J.;
Exchange Pathways of Doped Ag25 nanoclusters. Nanoscale 2016, 8, Orbulescu, J.; Micic, M.; Whyte, J. D.; Blackwelder, P.; Leblanc, R. M.
17333−17339. Human Insulin Fibril-assisted Synthesis of Fluorescent Gold Nano-

8263 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

clusters in Alkaline Media under Physiological Temperature. Colloids (535) Patel, S. A.; Richards, C. I.; Hsiang, J.-C.; Dickson, R. M.
Surf., B 2013, 105, 167−172. Water-Soluble Ag Nanoclusters Exhibit Strong Two-Photon-Induced
(516) Kawasaki, H.; Hamaguchi, K.; Osaka, I.; Arakawa, R. pH- Fluorescence. J. Am. Chem. Soc. 2008, 130, 11602−11603.
Dependent Synthesis of Pepsin-Mediated Gold Nanoclusters with (536) Yau, S. H.; Abeyasinghe, N.; Orr, M.; Upton, L.; Varnavski, O.;
Blue Green and Red Fluorescent Emission. Adv. Funct. Mater. 2011, Werner, J. H.; Yeh, H.-C.; Sharma, J.; Shreve, A. P.; Martinez, J. S.;
21, 3508−3515. Goodson Iii, T. Bright Two-photon Emission and ultra-fast Relaxation
(517) Kawasaki, H.; Yoshimura, K.; Hamaguchi, K.; Arakawa, R. Dynamics in a DNA-templated Nanocluster Investigated by ultra-fast
Trypsin-stabilized Fluorescent Gold Nanocluster for Sensitive and Spectroscopy. Nanoscale 2012, 4, 4247−4254.
Selective Hg2+ Detection. Anal. Sci. 2011, 27, 591−596. (537) Hori, H.; Yamamoto, Y.; Iwamoto, T.; Miura, T.; Teranishi, T.;
(518) Chaudhari, K.; Pradeep, T. Initial Growth Kinetics of Miyake, M. Diameter Dependence of Ferromagnetic Spin Moment in
Luminescent Quantum Clusters of Silver within Albumin Family Au Nanocrystals. Phys. Rev. B: Condens. Matter Mater. Phys. 2004, 69,
Protein Templates. J. Phys. Chem. C 2015, 119, 9988−9994. 174411.
(519) Baksi, A.; Mitra, A.; Mohanty, J. S.; Lee, H.; De, G.; Pradeep, (538) Crespo, P.; Litrán, R.; Rojas, T. C.; Multigner, M.; de la
T. Size Evolution of Protein-Protected Gold Clusters in Solution: A Fuente, J. M.; Sánchez-López, J. C.; García, M. A.; Hernando, A.;
Combined SAXS−MS Investigation. J. Phys. Chem. C 2015, 119, Penadés, S.; Fernández, A. Permanent Magnetism, Magnetic
2148−2157. Anisotropy, and Hysteresis of Thiol-Capped Gold Nanoparticles.
(520) Durgadas, C. V.; Sharma, C. P.; Sreenivasan, K. Fluorescent Phys. Rev. Lett. 2004, 93, 087204.
Gold Clusters as Nanosensors for Copper Ions in Live Cells. Analyst (539) Negishi, Y.; Tsunoyama, H.; Suzuki, M.; Kawamura, N.;
2011, 136, 933−940. Matsushita, M. M.; Maruyama, K.; Sugawara, T.; Yokoyama, T.;
(521) Hu, D.; Sheng, Z.; Gong, P.; Zhang, P.; Cai, L. Highly Selective Tsukuda, T. X-ray Magnetic Circular Dichroism of Size-Selected,
Fluorescent Sensors for Hg2+ based on Bovine Serum Albumin-capped Thiolated Gold Clusters. J. Am. Chem. Soc. 2006, 128, 12034−12035.
Gold Nanoclusters. Analyst 2010, 135, 1411−1416. (540) McCoy, R. S.; Choi, S.; Collins, G.; Ackerson, B. J.; Ackerson,
(522) Goswami, N.; Giri, A.; Bootharaju, M. S.; Xavier, P. L.; C. J. Superatom Paramagnetism Enables Gold Nanocluster Heating in
Pradeep, T.; Pal, S. K. Copper Quantum Clusters in Protein Matrix: Applied Radiofrequency Fields. ACS Nano 2013, 7, 2610−2616.
Potential Sensor of Pb2+ ion. Anal. Chem. 2011, 83, 9676−9680. (541) Yuan, X.; Tay, Y.; Dou, X.; Luo, Z.; Leong, D. T.; Xie, J.
(523) Song, X.-R.; Goswami, N.; Yang, H.-H.; Xie, J. Functionaliza- Glutathione-Protected Silver Nanoclusters as Cysteine-Selective
tion of Metal Nanoclusters for Biomedical Applications. Analyst 2016, Fluorometric and Colorimetric Probe. Anal. Chem. 2013, 85, 1913−
141, 3126−3140. 1919.
(524) Yang, X.; Wang, E. K. CHAPTER 5 Synthesis and Applications (542) Yuan, X.; Yeow, T. J.; Zhang, Q.; Lee, J. Y.; Xie, J. Highly
of Silver Nanoclusters Protected by Polymers, Protein, Peptide and Luminescent Ag+ Nanoclusters for Hg2+ ion Detection. Nanoscale
Short Molecules. In Functional Nanometer-Sized Clusters of Transition 2012, 4, 1968−1971.
Metals: Synthesis, Properties and Applications; The Royal Society of (543) Fang, J.; Li, J.; Zhang, B.; Yuan, X.; Asakura, H.; Tanaka, T.;
Chemistry: 2014; pp 100−130. Teramura, K.; Xie, J.; Yan, N. The Support Effect on the Size and
(525) Goswami, N.; Li, J.; Xie, J. Chapter 11 - Functionalization and Catalytic Activity of Thiolated Au25 Nanoclusters as Precatalysts.
Application. In Frontiers of Nanoscience; Tatsuya, T., Hannu, H., Eds.; Nanoscale 2015, 7, 6325−6333.
Elsevier: 2015; Vol. 9, pp 297−345. (544) Yoskamtorn, T.; Yamazoe, S.; Takahata, R.; Nishigaki, J.-i.;
(526) Pradeep, T.; Baksi, A.; Xavier, P. L. CHAPTER 7 Noble Metal Thivasasith, A.; Limtrakul, J.; Tsukuda, T. Thiolate-Mediated
Clusters in Protein Templates. In Functional Nanometer-Sized Clusters Selectivity Control in Aerobic Alcohol Oxidation by Porous Carbon-
of Transition Metals: Synthesis, Properties and Applications; The Royal Supported Au25 Clusters. ACS Catal. 2014, 4, 3696−3700.
Society of Chemistry: 2014; pp 169−225. (545) Choi, S.; Dickson, R. M.; Yu, J. Developing Luminescent Silver
(527) Philip, R.; Chantharasupawong, P.; Qian, H.; Jin, R.; Thomas, Nanodots for Biological Applications. Chem. Soc. Rev. 2012, 41, 1867−
J. Evolution of Nonlinear Optical Properties: From Gold Atomic 1891.
Clusters to Plasmonic Nanocrystals. Nano Lett. 2012, 12, 4661−4667. (546) Schmid, G. The Relevance of Shape and Size of Au55 Clusters.
(528) Knoppe, S.; Vanbel, M.; van Cleuvenbergen, S.; Vanpraet, L.; Chem. Soc. Rev. 2008, 37, 1909−1930.
Bürgi, T.; Verbiest, T. Nonlinear Optical Properties of Thiolate- (547) Shang, L.; Dong, S.; Nienhaus, G. U. Ultra-small Fluorescent
Protected Gold Clusters. J. Phys. Chem. C 2015, 119, 6221−6226. Metal Nanoclusters: Synthesis and Biological Applications. Nano
(529) Knoppe, S.; Häkkinen, H.; Verbiest, T. Nonlinear Optical Today 2011, 6, 401−418.
Properties of Thiolate-Protected Gold Clusters: A Theoretical Survey (548) Tan, X.; Jin, R. Ultrasmall Metal Nanoclusters for Bio-related
of the First Hyperpolarizabilities. J. Phys. Chem. C 2015, 119, 27676− Applications. Wiley Interdisciplinary Reviews: Nanomed. Nanobiotech.
27682. 2013, 5, 569−581.
(530) Russier-Antoine, I.; Bertorelle, F.; Vojkovic, M.; Rayane, D.; (549) Chen, X.; Zhou, Y.; Peng, X.; Yoon, J. Fluorescent and
Salmon, E.; Jonin, C.; Dugourd, P.; Antoine, R.; Brevet, P.-F. Non- Colorimetric Probes for Detection of thiols. Chem. Soc. Rev. 2010, 39,
linear Optical Properties of Gold Quantum Clusters. The smaller the 2120−2135.
better. Nanoscale 2014, 6, 13572−13578. (550) Saha, K.; Agasti, S. S.; Kim, C.; Li, X.; Rotello, V. M. Gold
(531) Day, P. N.; Pachter, R.; Nguyen, K. A.; Bigioni, T. P. Linear Nanoparticles in Chemical and Biological sensing. Chem. Rev. 2012,
and Nonlinear Optical Response in Silver Nanoclusters: Insight from a 112, 2739−2779.
Computational Investigation. J. Phys. Chem. A 2016, 120, 507−518. (551) Guan, G.; Zhang, S.-Y.; Cai, Y.; Liu, S.; Bharathi, M. S.; Low,
(532) Polavarapu, L.; Manna, M.; Xu, Q.-H. Biocompatible M.; Yu, Y.; Xie, J.; Zheng, Y.; Zhang, Y.-W.; Han, M.-Y. Convenient
Glutathione Capped Gold Clusters as one- and two-photon Excitation Purification of Gold Clusters by Co-precipitation for Improved
Fluorescence Contrast Agents for Live Cells Imaging. Nanoscale 2011, Sensing of Hydrogen Peroxide, Mercury ions and Pesticides. Chem.
3, 429−434. Commun. 2014, 50, 5703−5705.
(533) Olesiak-Banska, J.; Waszkielewicz, M.; Matczyszyn, K.; Samoc, (552) George, A.; Shibu, E. S.; Maliyekkal, S. M.; Bootharaju, M. S.;
M. A Closer Look at two-photon Absorption, Absorption Saturation Pradeep, T. Luminescent, Freestanding Composite Films of Au15 for
and Nonlinear Refraction in Gold Nanoclusters. RSC Adv. 2016, 6, Specific Metal Ion Sensing. ACS Appl. Mater. Interfaces 2012, 4, 639−
98748−98752. 644.
(534) Ramakrishna, G.; Varnavski, O.; Kim, J.; Lee, D.; Goodson, T. (553) Kobayashi, N.; Kamei, Y.; Shichibu, Y.; Konishi, K.
Quantum-Sized Gold Clusters as Efficient Two-Photon Absorbers. J. Protonation-Induced Chromism of Pyridylethynyl-Appended [core
Am. Chem. Soc. 2008, 130, 5032−5033. +exo]-Type Au8 Clusters. Resonance-Coupled Electronic Perturbation

8264 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

through π-Conjugated Group. J. Am. Chem. Soc. 2013, 135, 16078− (574) Huang, C.-C.; Lin, T.-Y.; Yu, W.-S.; Chen, C.-T.; Chang, H.-T.
16081. Time-Resolved Luminescence-Based Assay for Thyroglobulin. J.
(554) Mathew, A.; Sajanlal, P. R.; Pradeep, T. Selective Visual Biomed. Nanotechnol. 2009, 5, 579−585.
Detection of TNT at the Sub-Zeptomole Level. Angew. Chem., Int. Ed. (575) Chen, C.-T.; Chen, W.-J.; Liu, C.-Z.; Chang, L.-Y.; Chen, Y.-C.
2012, 51, 9596−9600. Glutathione-bound Gold Nanoclusters for Selective-binding and
(555) Shibu, E. S.; Pradeep, T. Quantum Clusters in Cavities: Detection of Glutathione S-transferase-fusion Proteins from Cell
Trapped Au15 in Cyclodextrins. Chem. Mater. 2011, 23, 989−999. Lysates. Chem. Commun. 2009, 7515−7517.
(556) Paau, M. C.; Lo, C. K.; Yang, X.; Choi, M. M. F. Synthesis of (576) Shiang, Y.-C.; Lin, C.-A.; Huang, C.-C.; Chang, H.-T. Protein
1.4 nm α-Cyclodextrin-Protected Gold Nanoparticles for Lumines- A-conjugated Luminescent Gold Nanodots as a label-free Assay for
cence Sensing of Mercury(II) with Picomolar Detection Limit. J. Phys. Immunoglobulin G in plasma. Analyst 2011, 136, 1177−1182.
Chem. C 2010, 114, 15995−16003. (577) Sharma, J.; Yeh, H.-C.; Yoo, H.; Werner, J. H.; Martinez, J. S.
(557) Guo, C.; Irudayaraj, J. Fluorescent Ag Clusters via a Protein- Silver Nanocluster Aptamers: in situ Generation of Intrinsically
Directed Approach as a Hg(II) Ion Sensor. Anal. Chem. 2011, 83, Fluorescent Recognition Ligands for Protein Detection. Chem.
2883−2889. Commun. 2011, 47, 2294−2296.
(558) Zhang, G.; Li, Y.; Xu, J.; Zhang, C.; Shuang, S.; Dong, C.; Choi, (578) Petty, J. T.; Sengupta, B.; Story, S. P.; Degtyareva, N. N. DNA
M. M. F. Glutathione-protected Fluorescent Gold Nanoclusters for Sensing by Amplifying the Number of Near-Infrared Emitting,
Sensitive and Selective Detection of Cu2+. Sens. Actuators, B 2013, 183, Oligonucleotide-Encapsulated Silver Clusters. Anal. Chem. 2011, 83,
583−588. 5957−5964.
(559) Huang, C.-C.; Yang, Z.; Lee, K.-H.; Chang, H.-T. Synthesis of (579) Luo, Z.; Zheng, K.; Xie, J. Engineering Ultrasmall Water-
Highly Fluorescent Gold Nanoparticles for Sensing Mercury(II). soluble Gold and Silver Nanoclusters for Biomedical Applications.
Angew. Chem., Int. Ed. 2007, 46, 6824−6828. Chem. Commun. 2014, 50, 5143−5155.
(560) Pu, K.-Y.; Luo, Z.; Li, K.; Xie, J.; Liu, B. Energy Transfer (580) Chen, D.; Luo, Z.; Li, N.; Lee, J. Y.; Xie, J.; Lu, J. Amphiphilic
between Conjugated-Oligoelectrolyte-Substituted POSS and Gold Polymeric Nanocarriers with Luminescent Gold Nanoclusters for
Nanocluster for Multicolor Intracellular Detection of Mercury Ion. J. Concurrent Bioimaging and Controlled Drug Release. Adv. Funct.
Phys. Chem. C 2011, 115, 13069−13075. Mater. 2013, 23, 4324−4331.
(561) Xie, J.; Zheng, Y.; Ying, J. Y. Highly Selective and Ultrasensitive (581) Zhang, X.-D.; Chen, J.; Luo, Z.; Wu, D.; Shen, X.; Song, S.-S.;
Detection of Hg2+ based on Fluorescence Quenching of Au Sun, Y.-M.; Liu, P.-X.; Zhao, J.; Huo, S.; Fan, S.; Fan, F.; Liang, X.-J.;
Nanoclusters by Hg2+-Au+ interactions. Chem. Commun. 2010, 46, Xie, J. Enhanced Tumor Accumulation of Sub-2 nm Gold Nano-
961−963. clusters for Cancer Radiation Therapy. Adv. Healthcare Mater. 2014, 3,
(562) Chen, W.; Tu, X.; Guo, X. Fluorescent Gold Nanoparticles-
133−141.
based Fluorescence Sensor for Cu2+ ions. Chem. Commun. 2009, (582) Zhang, X.-D.; Luo, Z.; Chen, J.; Shen, X.; Song, S.; Sun, Y.;
1736−1738.
Fan, S.; Fan, F.; Leong, D. T.; Xie, J. Ultrasmall Au10−12(SG)10−12
(563) Liu, S.; Lu, F.; Zhu, J.-J. Highly Fluorescent Ag Nanoclusters:
Nanomolecules for High Tumor Specificity and Cancer Radiotherapy.
Microwave-assisted Green Synthesis and Cr 3+ Sensing. Chem.
Adv. Mater. 2014, 26, 4565−4568.
Commun. 2011, 47, 2661−2663.
(583) Yu, Y.; New, S. Y.; Xie, J.; Su, X.; Tan, Y. N. Protein-based
(564) Liu, Y.; Ai, K.; Cheng, X.; Huo, L.; Lu, L. Gold-Nanocluster-
Fluorescent Metal Nanoclusters for Small Molecular Drug Screening.
Based Fluorescent Sensors for Highly Sensitive and Selective
Chem. Commun. 2014, 50, 13805−13808.
Detection of Cyanide in Water. Adv. Funct. Mater. 2010, 20, 951−956.
(584) Muthu, M. S.; Kutty, R. V.; Luo, Z.; Xie, J.; Feng, S.-S.
(565) Guo, W.; Yuan, J.; Wang, E. Oligonucleotide-stabilized Ag
Nanoclusters as Novel Fluorescence Probes for the Highly Selective Theranostic vitamin E TPGS Micelles of Transferrin Conjugation for
and Sensitive Detection of the Hg2+ ion. Chem. Commun. 2009, 3395− Targeted Co-delivery of Docetaxel and Ultra Bright Gold Nano-
3397. clusters. Biomaterials 2015, 39, 234−248.
(566) Roy, S.; Palui, G.; Banerjee, A. The as-prepared Gold Cluster- (585) Zhang, X.-D.; Luo, Z.; Chen, J.; Song, S.; Yuan, X.; Shen, X.;
based Fluorescent Sensor for the Selective Detection of As (III) Ions Wang, H.; Sun, Y.; Gao, K.; Zhang, L.; Fan, S.; Leong, D. T.; Guo, M.;
in Aqueous Solution. Nanoscale 2012, 4, 2734−2740. Xie, J. Ultrasmall Glutathione-Protected Gold Nanoclusters as Next
(567) Shang, L.; Dong, S. Silver Nanocluster-based Fluorescent Generation Radiotherapy Sensitizers with High Tumor Uptake and
Sensors for Sensitive Detection of Cu(II). J. Mater. Chem. 2008, 18, High Renal Clearance. Sci. Rep. 2015, 5, 8669.
4636−4640. (586) Yuan, X.; Setyawati, M. I.; Tan, A. S.; Ong, C. N.; Leong, D.
(568) Zhou, T.-y.; Lin, L.-p.; Rong, M.-c.; Jiang, Y.-q.; Chen, X. T.; Xie, J. Highly Luminescent Silver Nanoclusters with Tunable
Silver−Gold Alloy Nanoclusters as a Fluorescence-Enhanced Probe for Emissions: Cyclic Reduction-decomposition Synthesis and Antimicro-
Aluminum Ion Sensing. Anal. Chem. 2013, 85, 9839−9844. bial Properties. NPG Asia Mater. 2013, 5, e39.
(569) Triulzi, R. C.; Micic, M.; Giordani, S.; Serry, M.; Chiou, W.-A.; (587) Zhang, X.-D.; Luo, Z.; Chen, J.; Wang, H.; Song, S.-S.; Shen,
Leblanc, R. M. Immunoasssay based on the Antibody-conjugated X.; Long, W.; Sun, Y.-M.; Fan, S.; Zheng, K.; Leong, D. T.; Xie, J.
PAMAM-dendrimer-gold Quantum dot Complex. Chem. Commun. Storage of Gold Nanoclusters in Muscle Leads to their Biphasic in
2006, 5068−5070. Vivo Clearance. Small 2015, 11, 1683−1690.
(570) Yang, S. W.; Vosch, T. Rapid Detection of MicroRNA by a (588) Ackerson, C. J.; Powell, R. D.; Hainfeld, J. F. Site-specific
Silver Nanocluster DNA Probe. Anal. Chem. 2011, 83, 6935−6939. Biomolecule Labeling with Gold Clusters. Methods Enzymol. 2010,
(571) Huang, C.-C.; Chiang, C.-K.; Lin, Z.-H.; Lee, K.-H.; Chang, 481, 195−230.
H.-T. Bioconjugated Gold Nanodots and Nanoparticles for Protein (589) Shang, L.; Stockmar, F.; Azadfar, N.; Nienhaus, G. U.
Assays Based on Photoluminescence Quenching. Anal. Chem. 2008, Intracellular Thermometry by Using Fluorescent Gold Nanoclusters.
80, 1497−1504. Angew. Chem., Int. Ed. 2013, 52, 11154−11157.
(572) Huang, C.-C.; Chen, C.-T.; Shiang, Y.-C.; Lin, Z.-H.; Chang, (590) Lee, R. J.; Wang, S.; Low, P. S. Measurement of Endosome pH
H.-T. Synthesis of Fluorescent Carbohydrate-Protected Au Nanodots Following Folate Receptor-Mediated Endocytosis. Biochim. Biophys.
for Detection of Concanavalin A and Escherichia coli. Anal. Chem. Acta, Mol. Cell Res. 1996, 1312, 237−242.
2009, 81, 875−882. (591) Sun, C.; Yang, H.; Yuan, Y.; Tian, X.; Wang, L.; Guo, Y.; Xu,
(573) Huang, C.-C.; Hung, Y.-L.; Shiang, Y.-C.; Lin, T.-Y.; Lin, Y.-S.; L.; Lei, J.; Gao, N.; Anderson, G. J.; Liang, X.-J.; Chen, C.; Zhao, Y.;
Chen, C.-T.; Chang, H.-T. Photoassisted Synthesis of Luminescent Nie, G. Controlling Assembly of Paired Gold Clusters within
Mannose−Au Nanodots for the Detection of Thyroglobulin in Serum. Apoferritin Nanoreactor for in Vivo Kidney Targeting and Biomedical
Chem. - Asian J. 2010, 5, 334−341. Imaging. J. Am. Chem. Soc. 2011, 133, 8617−8624.

8265 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(592) Yamamura, T.; Ariyasu, S.; Sakamoto, R. Affinity Clusters: An (614) Jia, Q.; Zhao, D.; Tang, B.; Zhao, N.; Li, H.; Sang, Y.; Bao, N.;
Adenine-Coated Gold Cluster Binds to Thymine Loops in DNA. Zhang, X.; Xu, X.; Liu, H. Synergistic catalysis of Au-Cu/TiO2-NB
Chem. - Asian J. 2011, 6, 1761−1765. Nanopaper in Aerobic Oxidation of Benzyl Alcohol. J. Mater. Chem. A
(593) Tao, Y.; Li, Z.; Ju, E.; Ren, J.; Qu, X. Polycations-functionalized 2014, 2, 16292−16298.
Water-soluble Gold Nanoclusters: a Potential Platform for Simulta- (615) Larsen, S. C. Applications of Zeolite and Mesoporous Silica
neous Enhanced Gene Delivery and Cell Imaging. Nanoscale 2013, 5, Nanomaterials in Catalysis, Adsorption of Environmental Contami-
6154−6160. nants and Drug Delivery. Presented at the National Meeting of the
(594) Shang, L.; Nienhaus, G. U. Gold Nanoclusters as Novel American Chemical Society, 2014; Paper MWRM-243.
Optical Probes for in vitro and in vivo Fluorescence Imaging. Biophys. (616) Lehman, S. E.; Larsen, S. C. Zeolite and Mesoporous Silica
Rev. 2012, 4, 313−322. Nanomaterials: Greener Syntheses, Environmental Applications and
(595) Palmal, S.; Jana, N. R. Gold Nanoclusters with Enhanced Biological Toxicity. Environ. Sci.: Nano 2014, 1, 200−213.
Tunable Fluorescence as Bioimaging probes. Wiley Interdiscipl. Rev: (617) Liu, H.; Ye, F.; Yao, Q.; Cao, H.; Xie, J.; Lee, J. Y.; Yang, J.
Nanomed. Nanobiotech. 2014, 6, 102−110. Stellated Ag-Pt Bimetallic Nanoparticles: An Effective Platform for
(596) Chen, W.-Y.; Lin, J.-Y.; Chen, W.-J.; Luo, L.; Wei-Guang Diau, Catalytic Activity Tuning. Sci. Rep. 2015, 4, 3969.
E.; Chen, Y.-C. Functional Gold Nanoclusters as Antimicrobial agents (618) Majdalawieh, A.; Kanan, M. C.; El-Kadri, O.; Kanan, S. M.
for Antibiotic-resistant Bacteria. Nanomedicine 2010, 5, 755−764. Recent Advances in Gold and Silver nanoparticles: Synthesis and
(597) Anema, J. R.; Li, J.-F.; Yang, Z.-L.; Ren, B.; Tian, Z.-Q. Shell- Applications. J. Nanosci. Nanotechnol. 2014, 14, 4757−4780.
Isolated Nanoparticle-Enhanced Raman Spectroscopy: Expanding the (619) Morsy, S. M. I.; Shaban, S. A. Investigation of Ionic Liquid with
Versatility of Surface-Enhanced Raman Scattering. Annu. Rev. Anal. and without Suspension of Nanomaterials as Satalysis for Sulfur
Chem. 2011, 4, 129−150. Removal from Gas Oil at Room Temperature. Int. J. Curr. Microbiol.
(598) He, J.; Lin, X.-M.; Divan, R.; Jaeger, H. M. In-Situ Partial Appl. Sci. 2014, 3, 167−180.
Sintering of Gold-Nanoparticle Sheets for SERS Applications. Small (620) Rossi, L. M.; Costa, N. J. S.; Silva, F. P.; Wojcieszak, R.
2011, 7, 3487−3492. Magnetic Nanomaterials in Catalysis: Advanced Catalysts for Magnetic
(599) Kumar, G. V. P.; Shruthi, S.; Vibha, B.; Reddy, B. A. A.; Kundu, Separation and Beyond. Green Chem. 2014, 16, 2906−2933.
T. K.; Narayana, C. Hot Spots in Ag Core−Au Shell Nanoparticles (621) Varma, R. S. Magnetically Retrievable Nano-catalysts in Benign
Potent for Surface-Enhanced Raman Scattering Studies of Biomole- Media. Presented at the National Meeting of the American Chemical
cules. J. Phys. Chem. C 2007, 111, 4388−4392. Society, 2014; Paper COLL-689.
(600) Wang, Y.; Yan, B.; Chen, L. SERS Tags: Novel Optical (622) Zhang, Q.; Yin, Y. Nanomaterials Engineering and Applications
Nanoprobes for Bioanalysis. Chem. Rev. 2013, 113, 1391−1428. in catalysis. Pure Appl. Chem. 2014, 86, 53−69.
(601) Leng, W.; Vikesland, P. J. Nanoclustered Gold Honeycombs (623) Han, H.-L.; Melaet, G.; Alayoglu, S.; Somorjai, G. A. In Situ
for Surface-Enhanced Raman Scattering. Anal. Chem. 2013, 85, 1342− Microscopy and Spectroscopy Applied to Surfaces at Work.
1349.
ChemCatChem 2015, 7, 3625−3638.
(602) Chakraborty, I.; Bag, S.; Landman, U.; Pradeep, T. Atomically
(624) Merrill, N. A.; McKee, E. M.; Merino, K. C.; Drummy, L. F.;
Precise Silver Clusters as New SERS Substrates. J. Phys. Chem. Lett.
Lee, S.; Reinhart, B.; Ren, Y.; Frenkel, A. I.; Naik, R. R.; Bedford, N.
2013, 4, 2769−2773.
M.; Knecht, M. R. Identifying the Atomic-Level Effects of Metal
(603) Bisson, L.; Boissiere, C.; Sanchez, C.; Thomazeau, C.; Uzio, D.
Composition on the Structure and Catalytic Activity of Peptide-
New Palladium Nanomaterials for Catalysis: Mechanisms Controlling
Templated Materials. ACS Nano 2015, 9, 11968−11979.
Formation and Evolution of Nanostructures in a Seed-mediated
(625) Mori, K.; Tanaka, H.; Dojo, M.; Yoshizawa, K.; Yamashita, H.
Synthesis. MRS Online Proc. Libr. 2007, 1017, 1017-DD16-26.
(604) Louis, B.; Begin, D.; Ledoux, M.-J.; Pham-Huu, C. In Advances Synergic Catalysis of PdCu Alloy Nanoparticles within a Macro-
in the Use of Carbon Nanomaterials in Catalysis; Elsevier Ltd.: 2009; pp reticular Basic Resin for Hydrogen Production from Formic Acid.
621−649. Chem. - Eur. J. 2015, 21, 12085−12092.
(605) Viswanathan, B. The Science of Nanomaterials in Catalysis. (626) Philippot, K.; Lignier, P.; Chaudret, B. Organometallic
Chem. Ind. Dig. 2009, 22, 69−77. Ruthenium Nanoparticles and Catalysis. Top. Organomet. Chem.
(606) Wu, Y.; Yu, J.; Liu, H.-M.; Xu, B.-Q. One-dimensional TiO2 2014, 48, 319−370.
Nanomaterials: Preparation and Catalytic Applications. J. Nanosci. (627) Whitby, R. Nanomaterials in Catalysis edited by Philippe Serp
Nanotechnol. 2010, 10, 6707−6719. and Karine Philippot. Appl. Organomet. Chem. 2015, 29, 59.
(607) Banares, M. A. Operando Spectroscopy: the Knowledge Bridge (628) Yao, Q.; Lu, Z.-H.; Wang, Y.; Chen, X.; Feng, G. Synergetic
to Assessing Structure-Performance Relationships in Catalyst Nano- Catalysis of Non-noble Bimetallic Cu-Co Nanoparticles Embedded in
particles. Adv. Mater. 2011, 23, 5293−5301. SiO2 Nanospheres in Hydrolytic Dehydrogenation of Ammonia
(608) Li, Y.; Yang, X.-Y.; Feng, Y.; Yuan, Z.-Y.; Su, B.-L. One- Borane. J. Phys. Chem. C 2015, 119, 14167−14174.
Dimensional Metal Oxide Nanotubes, Nanowires, Nanoribbons, and (629) Zhang, D.-X.; Liu, J.; Zhang, H.-X.; Wen, T.; Zhang, J. A
Nanorods: Synthesis, Characterizations, Properties and Applications. Rational Strategy To Construct a Neutral Boron Imidazolate
Crit. Rev. Solid State Mater. Sci. 2012, 37, 1−74. Framework with Encapsulated Small-Size Au-Pd Nanoparticles for
(609) Smiljanic, M.; Srejic, I.; Grgur, B.; Rakocevic, Z.; Strbac, S. Catalysis. Inorg. Chem. 2015, 54, 6069−6071.
Catalysis of Hydrogen Evolution on Au(111) Modified by (630) Zhang, L.; Anderson, R. M.; Crooks, R. M.; Henkelman, G.
Spontaneously Deposited Pd Nanoislands. Electrocatalysis 2012, 3, Correlating Structure and Function of Metal Nanoparticles for
369−375. Catalysis. Surf. Sci. 2015, 640, 65−72.
(610) Bhatia, S. K.; Nicholson, D. Friction between Solids and (631) Zhang, S.; Nguyen, L.; Liang, J.-X.; Shan, J.; Liu, J.; Frenkel, A.
Adsorbed Fluids is Spatially Distributed at the Nanoscale. Langmuir I.; Patlolla, A.; Huang, W.; Li, J.; Tao, F. Catalysis on Singly Dispersed
2013, 29, 14519−14526. bimetallic sites. Nat. Commun. 2015, 6, 7938.
(611) Polshettiwar, V. Nanomaterials in Catalysis. Edited by Philippe (632) Zhong, L.; Anand, C.; Lakhi, K. S.; Lawrence, G.; Vinu, A.
Serp and Karine Philippot. Angew. Chem., Int. Ed. 2013, 52, 11199. Bifunctional Mesoporous Carbon Nitride: Highly Efficient Enzyme-
(612) Zhu, J.; Holmen, A.; Chen, D. Carbon Nanomaterials in like Catalyst for One-pot Deacetalization-Knoevenagel Reaction. Sci.
Catalysis: Proton Affinity, Chemical and Electronic Properties, and Rep. 2015, 5, 12901.
their Catalytic Consequences. ChemCatChem 2013, 5, 378−401. (633) Ansar, S. M.; Kitchens, C. L. The Impact of Gold Nanoparticle
(613) Dong, S. Research on Nanomaterials in the Chemical Aspects. Stabilizing Ligand on Colloidal Catalytic Reduction of 4-Nitrophenol.
Appl. Mech. Mater. 2014, 484−485, 118−121. ACS Catal. 2016, 6, 5553−5560.

8266 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(634) Bhosale, M. A.; Bhanage, B. M. A Simple Approach for (657) Zhu, Y.; Qian, H.; Jin, R. Catalysis opportunities of Atomically
Sonochemical Synthesis of Cu2O Nanoparticles with high Catalytic Precise Gold Nanoclusters. J. Mater. Chem. 2011, 21, 6793−6799.
Properties. Adv. Powder Technol. 2016, 27, 238−244. (658) Lewis, L. N. Chemical Catalysis by Colloids and Clusters.
(635) Huang, T.; Li, H.; Huang, L.; Li, S.; Li, K.; Zhou, Y. Hybrid Chem. Rev. 1993, 93, 2693−2730.
Vesicles with Alterable Fully Covered Armors of Nanoparticles: (659) Yamazoe, S.; Koyasu, K.; Tsukuda, T. Nonscalable Oxidation
Fabrication, Catalysis, and Surface-Enhanced Raman Scattering. Catalysis of Gold Clusters. Acc. Chem. Res. 2014, 47, 816−824.
Langmuir 2016, 32, 991−996. (660) Turner, M.; Golovko, V. B.; Vaughan, O. P. H.; Abdulkin, P.;
(636) Kudaibergenov, S. E.; Tatykhanova, G. S.; Selenova, B. S. Berenguer-Murcia, A.; Tikhov, M. S.; Johnson, B. F. G.; Lambert, R.
Polymer Protected and Gel Immobilized Gold and Silver Nano- M. Selective Oxidation with Dioxygen by Gold Nanoparticle Catalysts
particles in Catalysis. J. Inorg. Organomet. Polym. Mater. 2016, 26, Derived from 55-atom Clusters. Nature 2008, 454, 981−983.
1198−1211. (661) Andreiadis, E. S.; Vitale, M. R.; Mezailles, N.; Le Goff, X.; Le
(637) Livingston, C.; Metz, K. Developing a Sustainable Catalyst: Floch, P.; Toullec, P. Y.; Michelet, V. Chiral Undecagold Clusters:
Synthesis, Characterization, and Catalytic Application of Palladium Synthesis, Characterization and Investigation in Catalysis. Dalton
Nanoparticles in Carbon Microsphere Composites. Presented at the Trans. 2010, 39, 10608−10616.
National Meeting of the American Chemical Society, 2016; Paper (662) Kauffman, D. R.; Alfonso, D.; Matranga, C.; Qian, H.; Jin, R.
CHED-1177. Experimental and Computational Investigation of Au25 Clusters and
(638) Lu, Y.; Ballauff, M. Spherical Polyelectrolyte Brushes as CO2: A Unique Interaction and Enhanced Electrocatalytic Activity. J.
Nanoreactors for the Generation of Metallic and Oxidic Nanoparticles: Am. Chem. Soc. 2012, 134, 10237−10243.
Synthesis and Application in Catalysis. Prog. Polym. Sci. 2016, 59, 86− (663) Xie, S.; Tsunoyama, H.; Kurashige, W.; Negishi, Y.; Tsukuda,
104. T. Enhancement in Aerobic Alcohol Oxidation Catalysis of Au25
(639) Sakthikumar, K.; Ede, S. R.; Mishra, S.; Kundu, S. Shape- Clusters by Single Pd Atom Doping. ACS Catal. 2012, 2, 1519−1523.
selective Synthesis of Sn(MoO4)2 Nanomaterials for Catalysis and (664) Leelavathi, A.; Bhaskara Rao, T.; Pradeep, T. Supported
Supercapacitor Applications. Dalton Trans. 2016, 45, 8897−8915. Quantum Clusters of Silver as Enhanced Catalysts for Reduction.
(640) Walker, J. M.; Zaleski, J. M. A Simple Route to Diverse Noble Nanoscale Res. Lett. 2011, 6, 123.
Metal-decorated Iron Oxide Nanoparticles for Catalysis. Nanoscale (665) Jirkovský, J. S.; Panas, I.; Ahlberg, E.; Halasa, M.; Romani, S.;
2016, 8, 1535−1544. Schiffrin, D. J. Single Atom Hot-Spots at Au−Pd Nanoalloys for
(641) Yang, L.; Liu, X.; Lu, Q.; Huang, N.; Liu, M.; Zhang, Y.; Yao, S. Electrocatalytic H2O2 Production. J. Am. Chem. Soc. 2011, 133,
Catalytic and Peroxidase-like Activity of Carbon based-AuPd 19432−19441.
Bimetallic Nanocomposite Produced using Carbon Dots as the (666) Zhang, H.; Watanabe, T.; Okumura, M.; Haruta, M.; Toshima,
Reductant. Anal. Chim. Acta 2016, 930, 23−30. N. Catalytically Highly Active top Gold atom on Palladium
(642) Ye, L.; Wen, G.; Ouyang, H.; Liu, Q.; Liang, A.; Jiang, Z. A Nanocluster. Nat. Mater. 2012, 11, 49−52.
Novel and Highly Sensitive Nanocatalytic Surface Plasmon Reso- (667) Yuan, D.; Gong, X.; Wu, R. Atomic Configurations of Pd
nance-scattering Analytical Platform for Detection of Trace Pb Ions. Atoms in PdAu(111) Bimetallic Surfaces Investigated using the First-
Sci. Rep. 2016, 6, 24150. principles Pseudopotential Plane Wave Approach. Phys. Rev. B:
(643) Ye, R.; Hurlburt, T. J.; Sabyrov, K.; Alayoglu, S.; Somorjai, G. Condens. Matter Mater. Phys. 2007, 75, 085428.
A. Molecular Catalysis science: Perspective on Unifying the Fields of (668) Bi, X.; Wang, R.; Ding, Y. Boosting the Performance of Pt
Catalysis. Proc. Natl. Acad. Sci. U. S. A. 2016, 113, 5159−5166. Electro-catalysts toward formic acid Electro-oxidation by Depositing
(644) Yamazoe, S.; Koyasu, K.; Tsukuda, T. Nonscalable Oxidation sub-monolayer Au Clusters. Electrochim. Acta 2011, 56, 10039−10043.
Catalysis of Gold Clusters. Acc. Chem. Res. 2014, 47, 816−824. (669) Gao, Y.; Shao, N.; Pei, Y.; Chen, Z.; Zeng, X. C. Catalytic
(645) Zhu, Y.; Qian, H.; Drake, B. A.; Jin, R. Atomically Precise Activities of Subnanometer Gold Clusters (Au16−Au18, Au20, and
Au25(SR)18 Nanoparticles as Catalysts for the Selective Hydrogenation Au27−Au35) for CO Oxidation. ACS Nano 2011, 5, 7818−7829.
of α,β-Unsaturated Ketones and Aldehydes. Angew. Chem., Int. Ed. (670) Jena, N. K.; Chandrakumar, K. R. S.; Ghosh, S. K. Beyond the
2010, 49, 1295−1298. Gold−Hydrogen Analogy: Doping Gold Cluster with H-atom−O2
(646) Haruta, M.; Kobayashi, T.; Sano, H.; Yamada, N. Novel Gold Activation and Reduction of the Reaction Barrier for CO Oxidation. J.
Catalysts for the Oxidation of Carbon Monoxide at a Temperature far Phys. Chem. Lett. 2011, 2, 1476−1480.
Below 0° C. Chem. Lett. 1987, 16, 405−408. (671) Jena, N. K.; Chandrakumar, K. R. S.; Ghosh, S. K. DNA Base−
(647) Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. Gold Gold Nanocluster Complex as a Potential Catalyzing Agent: An
Catalysts Prepared by Coprecipitation for Low-temperature Oxidation Attractive Route for CO Oxidation Process. J. Phys. Chem. C 2012,
of Hydrogen and of Carbon Monoxide. J. Catal. 1989, 115, 301−309. 116, 17063−17069.
(648) Hashmi, A. S. K.; Hutchings, G. J. Gold Catalysis. Angew. (672) Liu, Y.; Tsunoyama, H.; Akita, T.; Xie, S.; Tsukuda, T. Aerobic
Chem., Int. Ed. 2006, 45, 7896−7936. Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters
(649) Mallat, T.; Baiker, A. Oxidation of Alcohols with Molecular on Hydroxyapatite: Size Effect in the Sub-2 nm Regime. ACS Catal.
Oxygen on Solid Catalysts. Chem. Rev. 2004, 104, 3037−3058. 2011, 1, 2−6.
(650) Jin, R. The Impacts of Nanotechnology on Catalysis by (673) Tenney, S. A.; Cagg, B. A.; Levine, M. S.; He, W.; Manandhar,
Precious Metal Nanoparticles. Nanotechnol. Rev. 2012, 1, 31−56. K.; Chen, D. A. Enhanced activity for supported Au clusters: Methanol
(651) Li, G.; Jin, R. Atomically Precise Gold Nanoclusters as New oxidation on Au/TiO2(110). Surf. Sci. 2012, 606, 1233−1243.
Model Catalysts. Acc. Chem. Res. 2013, 46, 1749−1758. (674) Veith, G. M.; Lupini, A. R.; Pennycook, S. J.; Dudney, N. J.
(652) Li, G.; Jin, R. Well-defined Gold Nanoclusters for Catalytic Influence of Support Hydroxides on the Catalytic Activity of Oxidized
Applications. RSC Catal. Ser. 2014, 18, 27−46. Gold Clusters. ChemCatChem 2010, 2, 281−286.
(653) Huang, J.; Haruta, M. Heterogeneous Catalysis by Gold (675) Gao, W.; Chen, X. F.; Li, J. C.; Jiang, Q. Is Au55 or Au38 Cluster
Clusters. In Bridging Heterogeneous and Homogeneous Catalysis; Wiley- a Threshold Catalyst for Styrene Epoxidation? J. Phys. Chem. C 2010,
VCH Verlag GmbH & Co. KGaA: 2014; pp 397−424. 114, 1148−1153.
(654) Yamazoe, S.; Tsukuda, T. Metal Clusters in Catalysis. RSC (676) Li, G.; Abroshan, H.; Liu, C.; Zhuo, S.; Li, Z.; Xie, Y.; Kim, H.
Smart Mater. 2014, 7, 291−322. J.; Rosi, N. L.; Jin, R. Tailoring the Electronic and Catalytic Properties
(655) Zhu, Y.; Qian, H.; Zhu, M.; Jin, R. Thiolate-Protected Aun of Au25 Nanoclusters via Ligand Engineering. ACS Nano 2016, 10,
Nanoclusters as Catalysts for Selective Oxidation and Hydrogenation 7998−8005.
Processes. Adv. Mater. 2010, 22, 1915−1920. (677) Maity, P.; Yamazoe, S.; Tsukuda, T. Dendrimer-Encapsulated
(656) Tsukuda, T.; Tsunoyama, H.; Sakurai, H. Aerobic Oxidations Copper Cluster as a Chemoselective and Regenerable Hydrogenation
Catalyzed by Colloidal Nanogold. Chem. - Asian J. 2011, 6, 736−748. Catalyst. ACS Catal. 2013, 3, 182−185.

8267 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

(678) Zhu, Y.; Wu, Z.; Gayathri, C.; Qian, H.; Gil, R. R.; Jin, R. (698) Herzing, A. A.; Kiely, C. J.; Carley, A. F.; Landon, P.;
Exploring Stereoselectivity of Au25 Nanoparticle Catalyst for Hydro- Hutchings, G. J. Identification of Active Gold Nanoclusters on Iron
genation of Cyclic ketone. J. Catal. 2010, 271, 155−160. Oxide Supports for CO Oxidation. Science 2008, 321, 1331−1335.
(679) Chaki, N. K.; Tsunoyama, H.; Negishi, Y.; Sakurai, H.; (699) Ma, G.; Binder, A.; Chi, M.; Liu, C.; Jin, R.; Jiang, D.-e.; Fan, J.;
Tsukuda, T. Effect of Ag-Doping on the Catalytic Activity of Polymer- Dai, S. Stabilizing Gold Clusters by Heterostructured Transition-metal
Stabilized Au Clusters in Aerobic Oxidation of Alcohol. J. Phys. Chem. Oxide-mesoporous Silica Supports for Enhanced Catalytic Activities
C 2007, 111, 4885−4888. for CO Oxidation. Chem. Commun. 2012, 48, 11413−11415.
(680) Chen, W.; Chen, S. Oxygen Electroreduction Catalyzed by (700) Liu, Y.; Tsunoyama, H.; Akita, T.; Tsukuda, T. Preparation of
Gold Nanoclusters: Strong Core Size Effects. Angew. Chem., Int. Ed. ∼ 1 nm Gold Clusters Confined within Mesoporous Silica and
2009, 48, 4386−4389. Microwave-Assisted Catalytic Application for Alcohol Oxidation. J.
(681) Kumar, S. S.; Kwak, K.; Lee, D. Amperometric Sensing Based Phys. Chem. C 2009, 113, 13457−13461.
on Glutathione Protected Au 25 Nanoparticles and Their pH (701) Li, G.; Liu, C.; Lei, Y.; Jin, R. Au25 Nanocluster-catalyzed
Dependent Electrocatalytic Activity. Electroanalysis 2011, 23, 2116− Ullmann-type Homocoupling Reaction of Aryl Iodides. Chem.
2124. Commun. 2012, 48, 12005−12007.
(682) Han, J.; Liu, Y.; Guo, R. Reactive Template Method to (702) Yu, C.; Li, G.; Kumar, S.; Kawasaki, H.; Jin, R. Stable
Synthesize Gold Nanoparticles with Controllable Size and Morphol- Au25(SR)18/TiO2 Composite Nanostructure with Enhanced Visible
ogy Supported on Shells of Polymer Hollow Microspheres and Their Light Photocatalytic Activity. J. Phys. Chem. Lett. 2013, 4, 2847−2852.
Application for Aerobic Alcohol Oxidation in Water. Adv. Funct. Mater. (703) Jeseentharani, V.; Pugazhenthiran, N.; Mathew, A.;
2009, 19, 1112−1117. Chakraborty, I.; Baksi, A.; Ghosh, J.; Jash, M.; Anjusree, G. S.;
(683) Villa, A.; Wang, D.; Su, D. S.; Prati, L. Gold Sols as Catalysts Deepak, T. G.; Nair, A. S.; Pradeep, T. Atomically Precise Noble Metal
for Glycerol Oxidation: The Role of Stabilizer. ChemCatChem 2009, 1, Clusters Harvest Visible Light to Produce Energy. ChemistrySelect
510−514. 2017, 2, 1454−1463.
(684) Miyamura, H.; Yasukawa, T.; Kobayashi, S. Aerobic Oxidative (704) Kogo, A.; Sakai, N.; Tatsuma, T. Photoelectrochemical
Esterification of Alcohols Catalyzed by Polymer-incarcerated Gold Analysis of Size-dependent Electronic Structures of Gold Clusters
Nanoclusters under Ambient Conditions. Green Chem. 2010, 12, 776− Supported on TiO2. Nanoscale 2012, 4, 4217−4221.
778. (705) Sakai, N.; Tatsuma, T. Photovoltaic Properties of Glutathione-
(685) Biffis, A.; Cunial, S.; Spontoni, P.; Prati, L. Microgel-stabilized Protected Gold Clusters Adsorbed on TiO2 Electrodes. Adv. Mater.
Gold Nanoclusters: Powerful “quasi-homogeneous” Catalysts for the 2010, 22, 3185−3188.
Aerobic Oxidation of Alcohols in Water. J. Catal. 2007, 251, 1−6. (706) Radich, J. G.; Dwyer, R.; Kamat, P. V. Cu2S Reduced Graphene
(686) Kanaoka, S.; Yagi, N.; Fukuyama, Y.; Aoshima, S.; Tsunoyama, Oxide Composite for High-Efficiency Quantum Dot Solar Cells.
H.; Tsukuda, T.; Sakurai, H. Thermosensitive Gold Nanoclusters
Overcoming the Redox Limitations of S2−/Sn2− at the Counter
Stabilized by Well-Defined Vinyl Ether Star Polymers: Reusable and
Electrode. J. Phys. Chem. Lett. 2011, 2, 2453−2460.
Durable Catalysts for Aerobic Alcohol Oxidation. J. Am. Chem. Soc.
(707) Li, L.; Yang, X.; Gao, J.; Tian, H.; Zhao, J.; Hagfeldt, A.; Sun, L.
2007, 129, 12060−12061.
Highly Efficient CdS Quantum Dot-Sensitized Solar Cells Based on a
(687) Wang, Y.; Yan, R.; Zhang, J.; Zhang, W. Synthesis of Efficient
Modified Polysulfide Electrolyte. J. Am. Chem. Soc. 2011, 133, 8458−
and Reusable Catalyst of Size-controlled Au Nanoparticles within a
8460.
Porous, Chelating and Intelligent Hydrogel for Aerobic Alcohol
(708) Santra, P. K.; Nair, P. V.; George Thomas, K.; Kamat, P. V.
Oxidation. J. Mol. Catal. A: Chem. 2010, 317, 81−88.
(688) Ishida, T.; Haruta, M. N-Formylation of Amines via the CuInS2-Sensitized Quantum Dot Solar Cell. Electrophoretic Deposi-
Aerobic Oxidation of Methanol over Supported Gold Nanoparticles. tion, Excited-State Dynamics, and Photovoltaic Performance. J. Phys.
ChemSusChem 2009, 2, 538−541. Chem. Lett. 2013, 4, 722−729.
(689) Sakurai, H.; Kamiya, I.; Kitahara, H.; Tsunoyama, H.; Tsukuda, (709) Abbas, M. A.; Kim, T.-Y.; Lee, S. U.; Kang, Y. S.; Bang, J. H.
T. Aerobic Oxygenation of Benzylic Ketones Promoted by a Gold Exploring Interfacial Events in Gold-Nanocluster-Sensitized Solar
Nanocluster Catalyst. Synlett 2009, 2009, 245−248. Cells: Insights into the Effects of the Cluster Size and Electrolyte on
(690) Sakurai, H.; Tsunoyama, H.; Tsukuda, T. Trans. Mater. Res. Solar Cell Performance. J. Am. Chem. Soc. 2016, 138, 390−401.
Soc. Jpn. 2006, 31, 521−524. (710) Kim, M. S.; Abbas, M. A.; Bang, J. H. Ag16(SG)9 Nanoclusters
(691) Kamiya, I.; Tsunoyama, H.; Tsukuda, T.; Sakurai, H. Lewis as a Light Harvester for Metal-Cluster-Sensitized Solar Cells. Bull.
Acid Character of Zero-valent Gold Nanoclusters under Aerobic Korean Chem. Soc. 2016, 37, 791−792.
Conditions: Intramolecular Hydroalkoxylation of Alkenes. Chem. Lett. (711) Li, M.; Liu, Q.; Jia, Z.; Xu, X.; Cheng, Y.; Zheng, Y.; Xi, T.;
2007, 36, 646−647. Wei, S. Graphene oxide/hydroxyapatite composite coatings fabricated
(692) Kitahara, H.; Kamiya, I.; Sakurai, H. Intramolecular Addition of by electrophoretic nanotechnology for biological applications. Carbon
Toluenesulfonamide to Unactivated Alkenes Catalyzed by Gold 2014, 67, 185−197.
Nanoclusters under Aerobic Conditions. Chem. Lett. 2009, 38, 908− (712) Gupta, S. S.; Sreeprasad, T. S.; Maliyekkal, S. M.; Das, S. K.;
909. Pradeep, T. Graphene from Sugar and its Application in Water
(693) Kitahara, H.; Sakurai, H. Gold Nanoclusters as a Catalyst for Purification. ACS Appl. Mater. Interfaces 2012, 4, 4156−4163.
Intramolecular Addition of Primary Amines to Unactivated Alkenes (713) Sen Gupta, S.; Chakraborty, I.; Maliyekkal, S. M.; Adit Mark,
under Aerobic Conditions. Chem. Lett. 2010, 39, 46−48. T.; Pandey, D. K.; Das, S. K.; Pradeep, T. Simultaneous
(694) Nie, X.; Zeng, C.; Ma, X.; Qian, H.; Ge, Q.; Xu, H.; Jin, R. Dehalogenation and Removal of Persistent Halocarbon Pesticides
CeO2-supported Au38(SR)24 Nanocluster Catalysts for CO Oxidation: from Water Using Graphene Nanocomposites: A Case Study of
a Comparison of Ligand-on and -off Catalysts. Nanoscale 2013, 5, Lindane. ACS Sustainable Chem. Eng. 2015, 3, 1155−1163.
5912−5918. (714) Allen, M. J.; Tung, V. C.; Kaner, R. B. Honeycomb Carbon: a
(695) Valden, M.; Lai, X.; Goodman, D. W. Onset of Catalytic Review of Graphene. Chem. Rev. 2010, 110, 132−145.
Activity of Gold Clusters on Titania with the Appearance of (715) Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.; Novoselov, K.
Nonmetallic Properties. Science 1998, 281, 1647−1650. S.; Geim, A. K. The Electronic Properties of Graphene. Rev. Mod. Phys.
(696) Liu, Y.; Tsunoyama, H.; Akita, T.; Tsukuda, T. Efficient and 2009, 81, 109−162.
Selective Epoxidation of Styrene with TBHP Catalyzed by Au25 (716) Geim, A. K.; Novoselov, K. S. The Rise of Graphene. Nat.
Clusters on Hydroxyapatite. Chem. Commun. 2010, 46, 550−552. Mater. 2007, 6, 183−191.
(697) Li, G.; Qian, H.; Jin, R. Gold Nanocluster-Catalyzed Selective (717) Wang, Y.; Chen, J. T.; Yan, X. P. Fabrication of Transferrin
Oxidation of Sulfide to Sulfoxide. Nanoscale 2012, 4, 6714−6717. Functionalized Gold Nanoclusters/graphene Oxide Nanocomposite

8268 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

for Turn-on Near-infrared Fluorescent Bioimaging of Cancer Cells and (738) Hakkinen, H.; Moseler, M.; Kostko, O.; Morgner, N.;
Small Animals. Anal. Chem. 2013, 85, 2529−2535. Hoffmann, M. A.; von Issendorff, B. Symmetry and Electronic
(718) Ge, S.; Yan, M.; Lu, J.; Zhang, M.; Yu, F.; Yu, J.; Song, X.; Yu, Structure of Noble-Metal Nanoparticles and the Role of Relativity.
S. Electrochemical Biosensor Based on Graphene Oxide−Au Nano- Phys. Rev. Lett. 2004, 93, 093401.
clusters Composites for L-cysteine Analysis. Biosens. Bioelectron. 2012, (739) Böhringer, M.; Morgenstern, K.; Schneider, W.-D.; Berndt, R.
31, 49−54. Separation of a Racemic Mixture of Two-Dimensional Molecular
(719) Yang, G.-H.; Shi, J.-J.; Wang, S.; Xiong, W.-W.; Jiang, L.-P.; Clusters by Scanning Tunneling Microscopy. Angew. Chem., Int. Ed.
Burda, C.; Zhu, J.-J. Fabrication of a Boron Nitride-gold Nanocluster 1999, 38, 821−823.
Composite and its Versatile Application for Immunoassays. Chem. (740) Chen, Q.; Frankel, D. J.; Richardson, N. V. Chemisorption
Commun. 2013, 49, 10757−10759. Induced Chirality: Glycine on Cu. Surf. Sci. 2002, 497, 37−46.
(720) Liu, X.; Wei, S.; Chen, S.; Yuan, D.; Zhang, W. Graphene- (741) Ortega Lorenzo, M. O.; Baddeley, C. J.; Muryn, C.; Raval, R.
multiwall Carbon Nanotube-Gold Nanocluster Composites Modified Extended Surface Chirality from Supramolecular Assemblies of
Electrode for the Simultaneous Determination of Ascorbic acid, Adsorbed Chiral Molecules. Nature 2000, 404, 376−379.
Dopamine, and Uric acid. Appl. Biochem. Biotechnol. 2014, 173, 1717− (742) Parschau, M.; Romer, S.; Ernst, K.-H. Induction of
1726. Homochirality in Achiral Enantiomorphous Monolayers. J. Am.
(721) Som, A.; Chakraborty, I.; Maark, T. A.; Bhat, S.; Pradeep, T. Chem. Soc. 2004, 126, 15398−15399.
Cluster-Mediated Crossed Bilayer Precision Assemblies of 1D (743) Varnholt, B.; Dolamic, I.; Knoppe, S.; Burgi, T. On the
Nanowires. Adv. Mater. 2016, 28, 2827−2833. Flexibility of the Gold-thiolate Interface: Racemization of the
(722) Knoppe, S.; Bürgi, T. Chirality in Thiolate-Protected Gold Au40(SR)24 Cluster. Nanoscale 2013, 5, 9568−9571.
Clusters. Acc. Chem. Res. 2014, 47, 1318−1326. (744) Knoppe, S.; Dolamic, I.; Dass, A.; Bürgi, T. Separation of
(723) He, X.; Wang, Y.; Jiang, H.; Zhao, L. Structurally Well-Defined Enantiomers and CD Spectra of Au40(SCH2CH2Ph)24: Spectroscopic
Sigmoidal Gold Clusters: Probing the Correlation between Metal Evidence for Intrinsic Chirality. Angew. Chem., Int. Ed. 2012, 51,
Atom Arrangement and Chiroptical Response. J. Am. Chem. Soc. 2016, 7589−7591.
138, 5634−5643. (745) Knoppe, S.; Wong, O. A.; Malola, S.; Hakkinen, H.; Burgi, T.;
(724) Pelayo, J. J.; Whetten, R. L.; Garzón, I. L. Geometric Verbiest, T.; Ackerson, C. J. Chiral Phase Transfer and Enantioenrich-
Quantification of Chirality in Ligand-Protected Metal Clusters. J. Phys. ment of Thiolate-Protected Au102 Clusters. J. Am. Chem. Soc. 2014,
Chem. C 2015, 119, 28666−28678. 136, 4129−4132.
(725) Aikens, C. M. Chapter 9 - Optical Properties and Chirality. In (746) Knoppe, S.; Kothalawala, N.; Jupally, V. R.; Dass, A.; Burgi, T.
Frontiers of Nanoscience; Tatsuya, T.; Hannu, H., Eds.; Elsevier: 2015; Ligand Dependence of the Synthetic Approach and Chiroptical
Properties of a Magic Cluster Protected with a Bicyclic Chiral
Vol. 9, pp 223−261.
(726) Gautier, C.; Burgi, T. Vibrational Circular Dichroism of N- Thiolate. Chem. Commun. 2012, 48, 4630−4632.
(747) Yao, H.; Saeki, M.; Kimura, K. Induced Optical Activity in
acetyl-l-cysteine protected gold nanoparticles. Chem. Commun. 2005,
Boronic-Acid-Protected Silver Nanoclusters by Complexation with
5393−5395.
Chiral Fructose. J. Phys. Chem. C 2010, 114, 15909−15915.
(727) Gautier, C.; Burgi, T. Chiral N-isobutyryl-cysteine Protected
(748) Dolamic, I.; Varnholt, B.; Burgi, T. Chirality Transfer from
Gold Nanoparticles: Preparation, Size Selection, and Optical Activity
Gold Nanocluster to Ndsorbate Evidenced by Vibrational Circular
in the UV-vis and Infrared. J. Am. Chem. Soc. 2006, 128, 11079−11087.
Dichroism. Nat. Commun. 2015, 6, 7117.
(728) Gautier, C.; Burgi, T. Chiral gold Nanoparticles. ChemPhy-
(749) Escalle, A. l.; Mora, G.; Gagosz, F.; Mézailles, N.; Le Goff, X.
sChem 2009, 10, 483−492. F.; Jean, Y.; Le Floch, P. Cationic Dimetallic Gold Hydride Complex
(729) Yao, H.; Fukui, T.; Kimura, K. Chiroptical Responses of d-/l-
Stabilized by a Xantphos-Phosphole ligand: Synthesis, X-ray Crystal
Penicillamine-Capped Gold Clusters under Perturbations of Temper- Structure, and Density Functional Theory Study. Inorg. Chem. 2009,
ature Change and Phase Transfer. J. Phys. Chem. C 2007, 111, 14968− 48, 8415−8422.
14976. (750) Tsui, E. Y.; Müller, P.; Sadighi, J. P. Reactions of a Stable
(730) Takano, S.; Tsukuda, T. Amplification of the Optical Activity Monomeric Gold(I) Hydride Complex. Angew. Chem., Int. Ed. 2008,
of Gold Clusters by the Proximity of BINAP. J. Phys. Chem. Lett. 2016, 47, 8937−8940.
7, 4509−4513. (751) Liu, C. W.; Lin, Y.-R.; Fang, C.-S.; Latouche, C.; Kahlal, S.;
(731) Lopez-Acevedo, O.; Tsunoyama, H.; Tsukuda, T.; Häkkinen, Saillard, J.-Y. [Ag7(H){E2P(OR)2}6] (E = Se, S): Precursors for the
H.; Aikens, C. M. Chirality and Electronic Structure of the Thiolate- Fabrication of Silver Nanoparticles. Inorg. Chem. 2013, 52, 2070−
Protected Au38 Nanocluster. J. Am. Chem. Soc. 2010, 132, 8210−8218. 2077.
(732) Gautier, C.; Bürgi, T. Vibrational Circular Dichroism of (752) Bootharaju, M. S.; Dey, R.; Gevers, L. E.; Hedhili, M. N.;
Adsorbed Molecules: BINAS on Gold Nanoparticles. J. Phys. Chem. C Basset, J.-M.; Bakr, O. M. A New Class of Atomically Precise, Hydride-
2010, 114, 15897−15902. Rich Silver Nanoclusters Co-Protected by Phosphines. J. Am. Chem.
(733) Humblot, V.; Haq, S.; Muryn, C.; Hofer, W. A.; Raval, R. From Soc. 2016, 138, 13770−13773.
Local Adsorption Stresses to Chiral surfaces: (R,R)-tartaric acid on (753) Zavras, A.; Khairallah, G. N.; Connell, T. U.; White, J. M.;
Ni(110). J. Am. Chem. Soc. 2002, 124, 503−510. Edwards, A. J.; Mulder, R. J.; Donnelly, P. S.; O’Hair, R. A. J. Synthesis,
(734) Garzón, I. L.; Beltrán, M. R.; González, G.; Gutıerrez- Structural Characterization, and Gas-Phase Unimolecular Reactivity of
González, I.; Michaelian, K.; Reyes-Nava, J. A.; Rodrıguez-Hernández, the Silver Hydride Nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2.
J. I. Chirality, Defects, and Disorder in Gold Clusters. Eur. Phys. J. D Inorg. Chem. 2014, 53, 7429−7437.
2003, 24, 105−109. (754) Zavras, A.; Ariafard, A.; Khairallah, G. N.; White, J. M.; Mulder,
(735) Garzón, I. L.; Reyes-Nava, J. A.; Rodríguez-Hernández, J. I.; R. J.; Canty, A. J.; O’Hair, R. A. J. Synthesis, Structure and Gas-phase
Sigal, I.; Beltrán, M. R.; Michaelian, K. Chirality in Bare and Passivated Reactivity of the Mixed Silver Hydride Borohydride Nanocluster
Gold Nanoclusters. Phys. Rev. B: Condens. Matter Mater. Phys. 2002, [Ag3(μ3-H)(μ3-BH4)LPh3]BF4 (LPh = bis(diphenylphosphino)-
66, 073403. methane). Nanoscale 2015, 7, 18129−18137.
(736) Santizo, I. E.; Hidalgo, F.; Perez, L. A.; Noguez, C.; Garzon, I. (755) Liao, P. K.; Fang, C. S.; Edwards, A. J.; Kahlal, S.; Saillard, J. Y.;
L. Intrinsic Chirality in Bare Gold Nanoclusters: The Au34− Case. J. Liu, C. W. Hydrido Copper Clusters Supported by Dithiocarbamates:
Phys. Chem. C 2008, 112, 17533−17539. Oxidative Hydride Removal and Neutron Diffraction Analysis of
(737) Lechtken, A.; Schooss, D.; Stairs, J. R.; Blom, M. N.; Furche, [Cu7(H){S2C(aza-15-crown-5)}6]. Inorg. Chem. 2012, 51, 6577−6591.
F.; Morgner, N.; Kostko, O.; von Issendorff, B.; Kappes, M. M. Au34−: (756) Latouche, C.; Kahlal, S.; Lin, Y.-R.; Liao, J.-H.; Furet, E.; Liu,
a chiral gold cluster. Angew. Chem., Int. Ed. 2007, 46, 2944−2948. C. W.; Saillard, J.-Y. Anion Encapsulation and Geometric Changes in

8269 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

Hepta- and Hexanuclear Copper(I) Dichalcogeno Clusters: A thesis and Selective Hydrogenation of 2-nitrobenzaldehyde. Nanoscale
Theoretical and Experimental Investigation. Inorg. Chem. 2013, 52, 2016, 8, 11371−11374.
13253−13262. (774) Chen, S.; Kimura, K. Synthesis of Thiolate-Stabilized Platinum
(757) Liao, P.-K.; Liu, K.-G.; Fang, C.-S.; Liu, C. W.; Fackler, J. P.; Nanoparticles in Protolytic Solvents as Isolable Colloids. J. Phys. Chem.
Wu, Y.-Y. A Copper(I) Homocubane Collapses to a Tetracapped B 2001, 105, 5397−5403.
Tetrahedron Upon Hydride Insertion. Inorg. Chem. 2011, 50, 8410− (775) Kawasaki, H.; Yamamoto, H.; Fujimori, H.; Arakawa, R.; Inada,
8417. M.; Iwasaki, Y. Surfactant-free Solution Synthesis of Fluorescent
(758) Dhayal, R. S.; Liao, J. H.; Lin, Y. R.; Liao, P. K.; Kahlal, S.; Platinum Subnanoclusters. Chem. Commun. 2010, 46, 3759−3761.
Saillard, J. Y.; Liu, C. W. A Nanospheric Polyhydrido Copper Cluster (776) Le Guével, X.; Trouillet, V.; Spies, C.; Jung, G.; Schneider, M.
of Elongated Triangular Orthobicupola Array: Liberation of H2 from Synthesis of Yellow-Emitting Platinum Nanoclusters by Ligand
Solar Energy. J. Am. Chem. Soc. 2013, 135, 4704−4707. Etching. J. Phys. Chem. C 2012, 116, 6047−6051.
(759) Crasto, D.; Dass, A. Green Gold: Au30(S-t-C4H9)18 Molecules. (777) Tanaka, S.-I.; Miyazaki, J.; Tiwari, D. K.; Jin, T.; Inouye, Y.
J. Phys. Chem. C 2013, 117, 22094−22097. Fluorescent Platinum Nanoclusters: Synthesis, Purification, Character-
(760) Buckart, S.; Ganteför, G.; Kim, Y. D.; Jena, P. Anomalous ization, and Application to Bioimaging. Angew. Chem., Int. Ed. 2011,
Behavior of Atomic Hydrogen Interacting with Gold Clusters. J. Am. 50, 431−435.
Chem. Soc. 2003, 125, 14205−14209. (778) Duchesne, P. N.; Zhang, P. Local Structure of Fluorescent
(761) Li, G.; Lei, Z.; Wang, Q.-M. Luminescent Molecular Ag−S Platinum Nanoclusters. Nanoscale 2012, 4, 4199−4205.
Nanocluster [Ag62S13(SBut)32](BF4)4. J. Am. Chem. Soc. 2010, 132, (779) Huang, X.; Ishitobi, H.; Inouye, Y. Formation of Fluorescent
17678−17679. Platinum Nanoclusters using Hyper-branched Polyethylenimine and
(762) Li, B.; Huang, R.-W.; Qin, J.-H.; Zang, S.-Q.; Gao, G.-G.; Hou, their Conjugation to Antibodies for Bio-imaging. RSC Adv. 2016, 6,
H.-W.; Mak, T. C. W. Thermochromic Luminescent Nest-Like Silver 9709−9716.
Thiolate Cluster. Chem. - Eur. J. 2014, 20, 12416−12420. (780) Chen, D.; Zhao, C.; Ye, J.; Li, Q.; Liu, X.; Su, M.; Jiang, H.;
(763) Sun, D.; Wang, H.; Lu, H.-F.; Feng, S.-Y.; Zhang, Z.-W.; Sun, Amatore, C.; Selke, M.; Wang, X. In Situ Biosynthesis of Fluorescent
G.-X.; Sun, D.-F. Two Birds with One Stone: Anion Templated Ball- Platinum Nanoclusters: Toward Self-Bioimaging-Guided Cancer
shaped Ag56 and Disc-like Ag20 Clusters. Dalton Transac. 2013, 42, Theranostics. ACS Appl. Mater. Interfaces 2015, 7, 18163−18169.
6281−6284. (781) Hackendorn, R. A.; Virkar, A. V. Synthesis of Platinum
(764) Fenske, D.; Persau, C.; Dehnen, S.; Anson, C. E. Syntheses and Nanoclusters and Electrochemical Investigation of their stability. J.
Crystal Structures of the Ag-S Cluster Compounds Power Sources 2013, 240, 618−629.
[Ag70S20(SPh)28(dppm)10] (CF3CO2)2 and (782) Takahashi, M.; Imaoka, T.; Hongo, Y.; Yamamoto, K.
[Ag262S100(StBu)62(dppb)6]. Angew. Chem., Int. Ed. 2004, 43, 305− Formation of a Pt12 Cluster by Single-Atom Control That Leads to
309. Enhanced Reactivity: Hydrogenation of Unreactive Olefins. Angew.
(765) Fenske, D.; Anson, C. E.; Eichhöfer, A.; Fuhr, O.; Ingendoh, Chem., Int. Ed. 2013, 52, 7419−7421.
A.; Persau, C.; Richert, C. Syntheses and Crystal Structures of (783) Imaoka, T.; Kitazawa, H.; Chun, W.-J.; Yamamoto, K. Finding
[Ag123S35(StBu)50] and [Ag344S124(StBu)96]. Angew. Chem., Int. Ed. the Most Catalytically Active Platinum Clusters With Low Atomicity.
2005, 44, 5242−5246. Angew. Chem., Int. Ed. 2015, 54, 9810−9815.
(766) Anson, C. E.; Eichhöfer, A.; Issac, I.; Fenske, D.; Fuhr, O.; (784) Yamamoto, K.; Imaoka, T.; Chun, W.-J.; Enoki, O.; Katoh, H.;
Sevillano, P.; Persau, C.; Stalke, D.; Zhang, J. Synthesis and Crystal Takenaga, M.; Sonoi, A. Size-specific Catalytic Activity of Platinum
Structures of the Ligand-Stabilized Silver Chalcogenide Clusters Clusters Enhances Oxygen Reduction Reactions. Nat. Chem. 2009, 1,
[Ag154Se77(dppxy)18], [Ag320(StBu)60S130(dppp)12], 397−402.
[Ag352S128(StC5H11)96], and [Ag490S188(StC5H11)114]. Angew. Chem., (785) Chen, S.; Huang, K.; Stearns, J. A. Alkanethiolate-Protected
Int. Ed. 2008, 47, 1326−1331. Palladium Nanoparticles. Chem. Mater. 2000, 12, 540−547.
(767) Manju, C. K.; Chakraborty, I.; Pradeep, T. Highly Luminescent (786) Clergeaud, G.; Genç, R.; Ortiz, M.; O’Sullivan, C. K.
Monolayer Protected Ag56Se13S15 clusters. J. Mater. Chem. C 2016, 4, Liposomal Nanoreactors for the Synthesis of Monodisperse Palladium
5572−5577. Nanoparticles Using Glycerol. Langmuir 2013, 29, 15405−15413.
(768) Li, X.; Guo, Z.; Xiao, C.; Goh, T. W.; Tesfagaber, D.; Huang, (787) Corthey, G.; Olmos-Asar, J. A.; Casillas, G.; Mariscal, M. M.;
W. Tandem Catalysis by Palladium Nanoclusters Encapsulated in Mejía-Rosales, S.; Azcárate, J. C.; Larios, E.; José-Yacamán, M.;
Metal−Organic Frameworks. ACS Catal. 2014, 4, 3490−3497. Salvarezza, R. C.; Fonticelli, M. H. Influence of Capping on the
(769) Mednikov, E. G.; Jewell, M. C.; Dahl, L. F. Nanosized (μ12- Atomistic Arrangement in Palladium Nanoparticles at Room Temper-
Pt)Pd164‑xPtx(CO)72(PPh3)20 (x ≈ 7) Containing Pt-Centered Four- ature. J. Phys. Chem. C 2014, 118, 24641−24647.
Shell 165-Atom Pd−Pt Core with Unprecedented Intershell Bridging (788) Corthey, G.; Rubert, A. A.; Picone, A. L.; Casillas, G.;
Carbonyl Ligands: Comparative Analysis of Icosahedral Shell-Growth Giovanetti, L. J.; Ramallo-López, J. M.; Zelaya, E.; Benitez, G. A.;
Patterns with Geometrically Related Pd145(CO)x(PEt3)30 (x ≈ 60) Requejo, F. G.; José-Yacamán, M.; Salvarezza, R. C.; Fonticelli, M. H.
Containing Capped Three-Shell Pd145 Core. J. Am. Chem. Soc. 2007, New Insights into the Chemistry of Thiolate-Protected Palladium
129, 11619−11630. Nanoparticles. J. Phys. Chem. C 2012, 116, 9830−9837.
(770) Mednikov, E. G.; Dahl, L. F. Syntheses, Structures and (789) Liu, Y.; Sun, C.; Bolin, T.; Wu, T.; Liu, Y.; Sternberg, M.; Sun,
Properties of Primarily Nanosized Homo/heterometallic Palladium S.; Lin, X.-M. Kinetic Pathway of Palladium Nanoparticle Sulfidation
CO/PR3 Ligated Ligands. Philos. Trans. R. Soc., A 2010, 368, 1301. Process at High Temperatures. Nano Lett. 2013, 13, 4893−4901.
(771) Erickson, J. D.; Mednikov, E. G.; Ivanov, S. A.; Dahl, L. F. (790) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.;
Isolation and Structural Characterization of a Mackay 55-Metal-Atom Nishihara, H. Preparation of Alkanethiolate-Protected Palladium
Two-Shell Icosahedron of Pseudo-Ih Symmetry, Pd55L12(μ3-CO)20 (L Nanoparticles and Their Size Dependence on Synthetic Conditions.
= PR3, R = Isopropyl): Comparative Analysis with Interior Two-Shell Langmuir 2002, 18, 1413−1418.
Icosahedral Geometries in Capped Three-Shell Pd145, Pt-Centered (791) Sadeghmoghaddam, E.; Gu, H.; Shon, Y.-S. Pd Nanoparticle-
Four-Shell Pd−Pt M165, and Four-Shell Au133 Nanoclusters. J. Am. Catalyzed Isomerization vs Hydrogenation of Allyl Alcohol: Solvent-
Chem. Soc. 2016, 138, 1502−1505. Dependent Regioselectivity. ACS Catal. 2012, 2, 1838−1845.
(772) Bhat, S.; Chakraborty, I.; Maark, T. A.; Mitra, A.; De, G.; (792) Sharma, S.; Kim, B.; Lee, D. Water-Soluble Pd Nanoparticles
Pradeep, T. Atomically Precise and Monolayer Protected Iridium Capped with Glutathione: Synthesis, Characterization, and Magnetic
Clusters in solution. RSC Adv. 2016, 6, 26679−26688. Properties. Langmuir 2012, 28, 15958−15965.
(773) Higaki, T.; Kitazawa, H.; Yamazoe, S.; Tsukuda, T. Partially (793) Yee, C. K.; Jordan, R.; Ulman, A.; White, H.; King, A.;
Oxidized Iridium Clusters within Dendrimers: Size-Controlled Syn- Rafailovich, M.; Sokolov, J. Novel One-Phase Synthesis of Thiol-

8270 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271
Chemical Reviews Review

Functionalized Gold, Palladium, and Iridium Nanoparticles Using

Superhydride. Langmuir 1999, 15, 3486−3491.
(794) Ramallo-López, J. M.; Giovanetti, L.; Craievich, A. F.; Vicentin,
F. C.; Marín-Almazo, M.; José-Yacaman, M.; Requejo, F. G. XAFS,
SAXS and HREM Characterization of Pd Nanoparticles Capped with
n-alkyl Thiol Molecules. Phys. B 2007, 389, 150−154.
(795) Zelakiewicz, B. S.; Lica, G. C.; Deacon, M. L.; Tong, Y. 13C
NMR and Infrared Evidence of a Dioctyl-disulfide Structure on
Octanethiol-protected Palladium Nanoparticle Surfaces. J. Am. Chem.
Soc. 2004, 126, 10053−10058.
(796) Corthey, G.; Rubert, A. A.; Picone, A. L.; Casillas, G.;
Giovanetti, L. J.; Ramallo-Lopez, J. M.; Zelaya, E.; Benitez, G. A.;
Requejo, F. G.; Jose-Yacaman, M.; Salvarezza, R. C.; Fonticelli, M. H.
New Insights into the Chemistry of Thiolate-Protected Palladium
Nanoparticles. J. Phys. Chem. C 2012, 116, 9830−9837.
(797) Zamborini, F. P.; Gross, S. M.; Murray, R. W. Synthesis,
Characterization, Reactivity, and Electrochemistry of Palladium
Monolayer Protected Clusters. Langmuir 2001, 17, 481−488.
(798) Negishi, Y.; Murayama, H.; Tsukuda, T. Formation of
Pdn(SR)m Clusters (n < 60) in the Reactions of PdCl2 and RSH (R
= n-C18H37, n-C12H25). Chem. Phys. Lett. 2002, 366, 561−566.
(799) Jia, X.; Li, J.; Wang, E. Cu Nanoclusters with Aggregation
Induced Emission Enhancement. Small 2013, 9, 3873−3879.
(800) Wu, Z.; Liu, J.; Gao, Y.; Liu, H.; Li, T.; Zou, H.; Wang, Z.;
Zhang, K.; Wang, Y.; Zhang, H.; Yang, B. Assembly-Induced
Enhancement of Cu Nanoclusters Luminescence with Mechanochro-
mic Property. J. Am. Chem. Soc. 2015, 137, 12906−12913.
(801) Salorinne, K.; Chen, X.; Troff, R. W.; Nissinen, M.; Hakkinen,
H. One-pot Synthesis and Characterization of Subnanometre-size
Benzotriazolate Protected Copper Clusters. Nanoscale 2012, 4, 4095−
4098.
(802) Goswami, N.; Baksi, A.; Giri, A.; Xavier, P. L.; Basu, G.;
Pradeep, T.; Pal, S. K. Luminescent Iron Clusters in Solution.
Nanoscale 2014, 6, 1848−1854.
(803) Marjomäki, V.; Lahtinen, T.; Martikainen, M.; Koivisto, J.;
Malola, S.; Salorinne, K.; Pettersson, M.; Häkkinen, H. Site-specific
Targeting of Enterovirus Capsid by Functionalized Monodisperse
Gold Nanoclusters. Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 1277−
1281.
(804) Habeeb Muhammed, M. A.; Pradeep, T. Au25@SiO2: Quantum
Clusters of Gold Embedded in Silica. Small 2011, 7, 204−208.
(805) Hassinen, J.; Pulkkinen, P.; Kalenius, E.; Pradeep, T.; Tenhu,
H.; Häkkinen, H.; Ras, R. H. A. Mixed-Monolayer-Protected Au25
Clusters with Bulky Calix[4]arene Functionalities. J. Phys. Chem. Lett.
2014, 5, 585−589.
(806) Chen, X.; Häkkinen, H. Protected but Accessible: Oxygen
Activation by a Calixarene-Stabilized Undecagold Cluster. J. Am. Chem.
Soc. 2013, 135, 12944−12947.
(807) de Silva, N.; Ha, J.-M.; Solovyov, A.; Nigra, M. M.; Ogino, I.;
Yeh, S. W.; Durkin, K. A.; Katz, A. A Bioinspired Approach for
Controlling Accessibility in Calix[4]arene-bound Metal Cluster
Catalysts. Nat. Chem. 2010, 2, 1062−1068.
(808) Antonello, S.; Dainese, T.; Pan, F.; Rissanen, K.; Maran, F.
Electrocrystallization of Monolayer-Protected Gold Clusters: Opening
the Door to Quality, Quantity, and New Structures. J. Am. Chem. Soc.
2017, 139, 4168−4174.

NOTE ADDED IN PROOF

Literature through December 2016 has been considered.
Certain new developments of 2017 are also mentioned. As
our review was getting ready for submission, a new review
appeared (ref 6). We direct the readers to this review for a
discussion of gold clusters, their structures, and additional
discussion on future possibilities in this field.

8271 DOI: 10.1021/acs.chemrev.6b00769

Chem. Rev. 2017, 117, 8208−8271