2010 Chem. Mater.

1995,7, 2010-2027

Reviews
Hybrid Inorganic-Organic Materials by Sol-Gel
Processing of Organofunctional Metal Alkoxides
Ulrich Schubert,” Nicola Husing, and Anne Lorenz
Institut f u r Anorganische Chemie der Technischen Universitat Wien, Getreidemarkt 9,
A-1060 Wien, Austria
Received June 13, 1995. Revised Manuscript Received September 8, 1995@

Metal alkoxides of t h e type (RO),E-X-A, where A represents a functional organic group,

and X is a hydrolytically stable spacer linking A and the metal alkoxide moiety E(OR’),, are
interesting precursors for t h e preparation of novel materials composed of both inorganic
and organic entities. The basic chemistry behind the preparation and the sol-gel processing
of these compounds is reviewed. The manifold options for chemical modification of both the
inorganic and the organic groups allow t h e deliberate preparation of materials with special
properties. Selected materials syntheses a r e discussed t o demonstrate the scope of possible
applications.

Introduction different properties on a nanoscopic level. Although

such materials are macroscopically homogeneous, their
A better understanding of the parameters governing properties reflect the nature of the chemical building
sol-gel chemistry, and the development of suitable blocks from which they are composed. The blending of
processing methods has led to the design of new materi- organic and inorganic components and the synergism
als with interesting properties in the past decade.’ of their properties in one material is particularly useful
Oxide materials of a variety of compositions are.now and allows the development of materials with totally
accessible as ceramic powders and fibers, glasses, thin new properties.
films, or coatings. Their development was possible only Organic groups in sol-gel materials can serve differ-
by learning how to deal with such key issues as the ent purposes:
control of the microstructure or the handling of multi- (i)During the preparation of purely inorganic materi-
component systems. While the early developments of als, they can control the reaction rates of the reactants,
the sol-gel process were mainly based on simple, the rheology of the sols, or the homogeneity and micro-
readily available precursors, the hugh potential of new structure of the derived gels. They are degraded during
precursors chemically tailored for special applications calcination to get purely inorganic materials.
is more and more realized.
(ii) The organic groups can be retained to modify or
Sol-gel chemistry not only offers an access to ceram- functionalize the oxidic material. The final material
ics and glasses with improved or new properties. The therefore is composed of inorganic (oxidic) structures
very mild reaction conditions, particularly the low cross-linked or substituted by organic groups. In this
reaction temperatures, also allow to incorporate organic article we will use the term “hybrid inorganic-organic
moieties in inorganic materials. This led to a conceptu- materials” for such materials,2 independent of the
ally novel class of materials composed of both inorganic function and structure of the organic groups.
and organic groupings. Hybrid inorganic-organic sol-gel materials can be
The classical approach to combine the properties of prepared by two approaches. Organic molecules can be
different materials led to the development of composite just embedded into an inorganic material, or vice versa.
materials or blends, where two different phases with Alternatively, the organic and inorganic groupings can
complementary physical properties are combined. The be linked by stable chemical bonds. The latter approach
concept of composites originated in the idea of producing requires precursors in which the organic group (R) is
materials having better properties than either of the two bonded to the oxide-formingelement (E) in a hydrolyti-
components. The chemical equivalent to composite cally stable way. The general process is outlined in eq
materials is the combination of chemical groupings with 1 for metal alkoxides, the most commonly used type of
precursors in sol-gel processes. Although the following
@ Abstract published in Advance ACSAbstracts, November 1,1995.
(1) Hench, L. L.; West, J. K. Chem. Rev. 1990,90, 33. Brinker, C.
J.; Scherer, G. Sol-Gel-Science,the Physics and Chemistry of Sol-Gel ( 2 ) Review articles: (a) Sanchez, C.; Ribot, F. New J . Chem. 1994,
Processing; Academic Press: London, 1990. Sakka, S.;Yoko, T. Struct. 18, 1007. (b) Novak, B. M. Adu. Mater. 1993, 5, 422. (c) Schottner,
Bonding 1992, 77, 89. Sol-Gel Technology for T h i n Films, Fibers, G.; Rose, K.; Schubert, U. Adu. in Science and Technology, 10.
Preforms, Electronics and Speciality Shapes; Klein, L. C., Ed.; Noyes: Intelligent Materials and Systems; Vincenzini, P., Ed.; Techna Srl.:
Park Ridge, 1988. Sol-Gel Optics: Processing and Applications; Klein, 1995; p 251. Cerveau, G.; Chorro, C.; Corriu, R.; Lepeytre, C.; LBre-
L. C., Ed.; Kluwer Academic: 1994. Chemistry, Spectroscopy, and Porte, J. P.; Moreau, J.; Thepot, P.; Wong Chi Man, M. I n Hybrid
Applications of Sol-Gel Glasses; Reisfeld, R., Jorgenson, C. K., Eds.; Organic-Inorganic Composites; Mark, J. E., Lee, C. Y.-C., Bianconi,
Springer: Berlin, 1992. P. A,, Eds.; A C S S y m p . Ser. 585: Washington, 1995; p 210.

0897-4756/95/2807-2010$09.00/0 0 1995 American Chemical Society

Reviews Chem. Mater., Vol. 7, No. 11, 1995 2011

discussion concentrates on alkoxide derivatives the arbitrary. For instance, simple alkyl or aryl groups,
same reasoning is valid for other hydrolyzable com- usually not being considered “functional groups”, may
pounds. have a n important “function” in some materials, besides

+ yE(OR), + zH20- R,EO, + w R O H

being a network modifier. The following example may
xRE(OR), illustrate this point. Silica aerogels made of only
(1) Si(OR14 are very hydrophilic, due to residual Si-OR
and Si-OH groups. However, the use of RSi(OMes)/
There is a huge variety of possibilities for the modi- Si(OMe)4 mixtures (R = alkyl or aryl) resulted in
fication of organic-inorganic hybrid materials: hydrophobic silica aerogels, being insensitive toward
(1)Variation of the Element E. In principle, any moisture. This hydrophobizing effect of the organic
element E (or combinations of different elements in groups is caused by the suppression and replacement
multicomponent systems) for which compounds suitable of the Si-OMe and Si-OH group^.^
for sol-gel processing are available can be used for the
formation of the inorganic structures. For the reasons Precursors
discussed below, silicon is currently the most often used
element. Alkoxysilane Derivatives. Organically substituted
(2) Variation of the Organic Group R. The choice alkoxysilanes of the type (R0)3Si-X-A (21, with a great
of the organic group R is nearly unlimited. The only variety of groups A are commercially available or easily
condition is that the group is hydrolytically stable or prepared. Si-C bonds are not hydrolyzed, due to the
reacts with water in a controlled way. The crucial specific properties of silicon (low Lewis acidity, rather
question is, of course, the hydrolytic stability of the E-R unpolar Si-C bond). Therefore, the functional group
link (vide infra). More than one organic group R can A can be linked to the silicon atom via a Si-C bond. In
be bonded to the same atom E, although such precursors the most common alkoxysilanes of the type 2, the spacer
are only rarely used in sol-gel chemistry. X is a (CH& ( p = 2, 3) chain. They have found
(3) Variation of x:y (Eq 11, the Ratio between the widespread industrial applications, for instance, in
Substituted and Unsubstituted Precursor. With silicones, a s adhesion promotors, for derivatizing sur-
decreasing x , the hybrid materials become “more inor- faces, or for the immobilization of substrates.
ganic”, and vice versa. The case y = 0 corresponds to a The preparation of such compounds has been re-
one-component system with RE(OR), as the only pre- viewed e l ~ e w h e r e .The
~ more general routes are sum-
cursor. For example, the silsesquioxanes RSiO1.5 are marized in Eqs 2-5.
formed upon sol-gel processing of RSi(OR)3, while The hydrosilylation of alkenes or alkynes, i.e., the
processing of a 1:4 mixture of RSi(OR13 and Si(OR14 addition of Si-H bonds to double or triple bonds, is one
gives a material with the “more inorganic” composition of the few general methods for the formation of Si-C
Ro.2Si01.9. Mixtures of more than two precursors of bonds. HSiCl3 is preferentially used for the industrial
course can also be employed. preparation of alkoxysilanes 2. The trichlorosilyl de-
The organic group R can have different functions; the rivatives C13Si-CH2-CH2-X-A are then converted to
most general is that of a network modifier. If an alkoxy the corresponding trialkoxysilyl derivatives (eq 2).
group in E(OR), is replaced by one or more hydrolyti-
cally stable groups R, the degree of cross-linking of the
oxide network, formed during sol-gel processing, de-
C1,Si-H + CH2=CH-X-A - +ROW-HCl
C13Si-CH2-CH2-X-A
creases. The physical consequences of such a substitu-
tion are very well-known from silicones. If the com- (RO),Si-CH2-CH2-X-A (2)
pounds RE(OR), are used as network modifiers, only
simple organic groups are necessary, such as alkyl or For instance, the technically very important silanes
aryl groups. (R0)3Si(CH2)3Clor (R0)3Si(CH2)2CNare prepared that
A more challenging possibility is the use of precursors way, starting from allyl chloride or acrylonitrile, re-
in which the organic group R bears some functionality. spectively. The hydrosilylation of allyl or vinyl com-
The relevant precursors are of the type (RO),E-X-A pounds directly with (R013SiH instead of C13SiH re-
(11, where A represents the functional organic group, quires more extensive safety efforts. It is technically
and X is a chemically inert spacer linking A and the mainly used for the preparation of (R0)3Si(CH2)3-
metal alkoxide moiety. Precursors with a direct chemi-
cal bond between A and E(OR), (without a spacer) OCH2CH-CH20 (GLYMO) and (R’O)3Si(CH2)3OC(O)C-
usually cannot be employed for chemical reasons. (CH3)=CH2 (MEMO) from allyl glycidyl ether or allyl
This review article is limited to materials made from methacrylate.
precursors of the type 1. Therefore, materials in which Only few alkenyl compounds with functional groups
functional compounds (dye molecules, catalysts, en- are accessible by the direct route shown in eq 2.
zymes, etc.) are just embedded in sol-gel matrixes will Therefore, substitution of a group A by another group
not be considered. We restrict ourselves to materials
in which the chemically bonded functional organic ( 3 ) Schwertfeger, F.; Glaubitt, W.; Schubert, U. J . Non-Cryst. Solids
1992, 145, 85. Schwertfeger, F.; Hiising, N.; Schubert, U. J . Sol-Gel
moieties are retained in the final material. We also Sci. Technol. 1994, 2, 103. Schwertfeger, F.; Emmerling, A,; Gross,
exclude the sol-gel synthesis of organic-inorganic J.;Schubert, U.; Fricke, J. Sol-Gel Processing and Applications; Attia,
hybrid polymers from E(OR),-terminated organic mac- Y. A,, Ed.; Plenum: New York, 1994; p 351. Schubert, U.; Schwert-
feger, F.; Hiising, N.; Seyfried, E. Mater. Res. SOC.Symp. Proc. 1994,
romolecules because this was recently reviewed 346, 151. Hiising, N.; Schwertfeger, F.; Tappert, W.; Schubert, U. J .
elsewhere.2asb Non-Cryst. Solids 1995, 186, 37.
(4)Noll, W. Chemie und Technologie der Silicone; Verlag Chemie:
The term “functional group” is difficult to delimit, and Weinheim, 1968. Deschler, U.; Kleinschmit, P.; Panster, P. Angew.
the choice of our examples is therefore somewhat Chem. 1986, 98, 237;Angew. Chem., Int. E d . Eng. 1986,25, 236.
2012 Chem. Mater., Vol. 7, No. 11, 1995 Reviews

30 3b

0 e1 4
0

s-si (OR),
:s 5

Figure 1. Selection of compounds of the type (R0)3Si-X-A (2) in which A is a polymerizable group.

A (eq 3) or chemical modification of a functional group OC(O)CH=CH213, was reacted with one equivalent of
(eq 4) often is the easier way to anchor more complex (R'0)3Si(CH2)3SHor (R'0)3SiH, respectively, to give the
functional groups to silicon. Many silanes of the type compounds 3a,ba6 The acrylate substituted silane 4
2 are industrially prepared by substitution of the (with a very long spacer between the double bond and
chloride in ( R O ) ~ S ~ ( C H Z )For
~ Cexample,
~.~ the techni- the (RO)3Si group) was similarly synthesized by the
cally important thio-substituted compound [(EtOhSi- thiol addition to the ethoxylated bisphenol-A diacrylate
(CHz)3]zS4(used a s adhesion promoter between rubber Me2C [C~H~OCHZCHZOC(O)CH=CH~IZ.~ Coupling of
and silica fillers) is prepared by reaction of (Et0)sSi- (Et0)3Si(CHz)3NCOwith OH-terminated bis(acry1ates)
(CHz)&l (A = C1) with Na2S4 ( A = S4).4,5 Examples is another efficient way to prepare precursors of this
for the modification by addition reactions to functional type.8
groups A (eq 41,such as (meth)acrylate, isocyanate or Other reactive groups suitable for organic crosslinking
epoxide groups, are given below. by polymerization reactions can, of course, be linked to
(RO)3Si-(CH,)p-A +A - the hydrolyzable (R'OI3Si group by the same methods.
One example is the silane 5 (Figure 1). Ring-opening
(R'0)3Si-(CHz)p-A +A (3) polymerization of its spiro orthoester moiety proceeds

(R'O)3Si-(CHz)p-A + Y-X-A - with only a very low shrinkage. The precursor silane
was prepared by addition of butyrolactone to the epoxy
group of GLYMO.~
(R0)3Si-(CHz),-A(Y)-X-A (4)
Another subset of compounds of the type 2, which
More recently, substitution of (R'0)3SiCl by Grignard recently has gained much interest in sol-gel chemistry
or organolithium reagents was used to prepare, for are those in which the functional group A is a chro-
instance, phenylene- or thiophenylene-bridged alkoxy- mophore. The examples in Figure 2 were also selected
silanes (eq 5). to represent the different preparative methods by which

(RO),SiCl+ MR - (RO),Si-R + MX (5)

(R'0)sSi-terminated groups can be introduced into more
complex organic moieties, such as dye molecules.
The alkoxysilane terminated azobenzenes 6a and 6b
The exhaustive coverage of all known organofunc- contain the same nonlinear optic (NLO) chromophore.
tional alkoxysilanes of the type 2 would exceed the scope However, different functionalities were used anchoring
of this article. We therefore restrict ourselves to a few a (R0)3Si-containingmoiety according to eq 4. For the
typical and topical examples. A selection is given in preparation of 6a (and related compounds), the N(R)-
Figures 1-4. We want to illustrate the point that CH2CH20H group of the dye (disperse red) was added
nearly any organic (or organometallic) group can be to the isocyanate group of ( R ' O ) ~ S ~ ( C H Z ) ~ N C O , ~ ~ - ~ ~
anchored to a n alkoxysilyl moiety by one of these while compound 6b was obtained by coupling of the
methods. NHz-substituted dye with the epoxy group of GLYM0.15
Alkoxysilanes, in which A is a reactive double bond Multiple substitution is also feasible, as exemplified by
(Figure l), are extremely interesting for the synthesis
of inorganic-organic polymers by polymerization of the (6) Wolter, H.; Glaubitt, W.; Rose, K. Muter. Res. SOC.Proc. 1992,
organic groups. In this approach, an organic network 271, 719.
is formed in the matrix of the primarily formed inor- (7) Rose, K.; Wolter, H.; Glaubitt, W. Muter. Res. Soc. Proc. 1992,
ganic network. The methacrylate substituted silane 271, 731.
( 8 ) Wolter, H.; Storch, W.; Ott, H. Muter. Res. SOC.Proc. 1994, 346,
( R O ) ~ S ~ ( C H Z ) ~ O C ( O ) C ( C H ~ ) =o C
r Hvinyltrialkoxy-
Z 143.
silane are very often used for this purpose (vide infra). (9) Wolter, H.; Storch, W. J . Sol-Gel Sei. Technol. 1994, 2, 93.
(10) Steins, H. Ph.D. Thesis, Universitat Wurzburg, 1994.
Recently, a class of compounds was developed that (11) Chaput, F.; Riehl, D.; Levy, Y.; Boilot, J. P. Chem. Muter. 1993,
allows easy variations in the organic chain of the hybrid 5, 589. Chaput, F.; Boilot, J. P.; Riehl, D.; Levy, Y. J . Sol-Gel Sei.
polymer, particularly to achieve a higher degree of cross- Technol. 1994, 2, 779.
(12) Lebeau, B.; Guermeur, C.; Sanchez, C. Mater. Res. SOC.Symp.
linking. The general idea is to use one double bond of Proc. 1994, 346, 315.
a n organic monomer with more than one acrylate (13) Ueda, M.; Kim, H.-B.; Ikeda, T.; Ichimura, K. J . Non-Cryst.
function to anchor the Si(OR'I3group and still have the Solids 1993, 163, 125.
(14) Yang, Z.; Xu, C.; Wu, B.; Dalton, L. R.; Kalluri, S.; Steier, W.
other double bond(s) available for a later polymerization. H.; Shi, Y.; Bechtel, J. H. Chem. Muter. 1994, 6 , 1899.
For instance, trimethylol-propanetriacrylate, EtC [CHz- (15) Jeng, R. J.; Chen, Y. M.; Jain, A. K.; Kumar, J.; Tripathy, S.
K. Chem. Muter. 1992, 4 , 972. Tripathy, S. K.; Kumar, J.; Chen, J.
T.; Marturunkalkul, S.; Jung, R. J.; Li, L.; Jiang, X. L. Muter. Res.
( 5 ) FehBr, F.; Berthold, H. J. Z . Anorg. Allg. Chem. 1953,273, 144. Soc. S y m p . Proc. 1994, 346, 531.
Reviews Chem. Mater,, Vol. 7, No. 11, 1995 2013

02N 4 N H(CH2)3Si(OEt),

7a

%
N 0 (CH,),Si(OMe)3

7b

~OC(0)-NH-(CHz)3Si(OEt)3

DNaNJ3 BC
~OC(O)-NH-(CH,),Si(OEt),

(EtO),(CH3,-NH-C(O)O(CH,)2 02 S Si (OMe),

@ a
Figure 2. Selection of compounds of the type (R0)3Si-X-A (2) in which A is a chromophore.

6c and related compounds.12-14 The alkoxysilyl-sub-

stituted NLO dyes 7a16 and 7b17 were prepared by ,.
substitution reactions according to eq 3 starting from 8 9
(R'0)3Si(CH2)3Cl, and the pyrene derivative 8, a fluo-
rescent dye, according to eq 5.18 Phenoxazinium and
Si(OR'),
phenazinium dyes with (aminopropy1)triethoxysilyl sub-
Fe
stituents, used for the coloration of glass, were simply (R'O),Si e
obtained by reaction of the corresponding parent dye
with (aminopropy1)trietho~ysilane.~~ 11
10
Metal complex fragments are other "functional groups"
in compounds of the type 2 with a very promising
potential for materials synthesis. The most common
method to prepare alkoxysilyl derivatives of metal
complexes is by ligand exchange (eq 6). In these reac-

m(RO),Si-X-A + ML, - Figure 3. Selection of compounds 2 in which A is a metal

[(RO)3Si-X-AJ,ML,-, + mL (6)
complex fragment.

of the possibilities to connect trialkoxysilyl groups and

tions, one or more ligands L are replaced by functional transition metals.
alkoxysilanes 2, in which the group A is capable of In principle, (R'OI3Si containing groups can be an-
coordinating metal complex fragments (ML,) or metal chored to nearly any organic entity by one of the
ions. The chemistry of such complexes was mainly discussed methods. Figure 4 shows some additional
developed with regard to the heterogenization of cata- examples of organofunctional alkoxysilanes tailored for
lytically active metal complexes by anchoring them on some special use. For instance, the ethoxysilyl-substi-
silica as a solid support.2o The use of the complexes tuted diamine 14 was used for the preparation of a
[(R'O)3Si-X-A],MLfl-, in sol-gel chemistry to prepare (EtO)3Si-substituted polyimide (eventually leading to
catalysts has recently been reviewed.21 The examples polyimide-silica hybrid material^),^^ the substituted
(9,22 11,2612,241325)in Figure 3 illustrate some crown ether 15 for facilitated transport membranes,28
and the silane 16 (and related single- and triple-chain
116) Commerciallv available from ABCR C o m a compounds) for immobilized amphiphilic monolayers on
(17) Nosaka, Y.; T"ohriiwa, N.; Kobayashi, T.; Fijii, N. Chem. Muter.
1993,5,930. glass plates.29 For the preparation of 16 a coupling
(18) Chambers, R. C.; Haruvy, Y.; Fox, M. A. Chem. Muter. 1994,
6, 1351.
(19) Nakazumi, H.; Amano, S. J . Chem. SOC., Chem. Comm. 1992, (24) Capka, M.; Czakoova, M.; Urbaniak, W.; Schubert, U. J . Mol.
1079. Nakazumi, H.; Amano, S.; Sakai, K. SPIE, Sol-Gel Opt. 1992, Cutul. 1992,74,335.
2288,356. (25) Breitscheidel, B.; Zieder, J.;Schubert, U. Chem. Muter. 1991,
(20) Leading references: Hartley, F. R. Supported Metal Complexes; 3, 559. Schubert, U.; Breitscheidel, B.; Buhler, H.; Egger, Ch.;
Reidel: Dordrecht, 1985. Yermakov, Yu. I.; Kuznetsov, B. N.; Za- Urbaniak, W. Muter. Res. SOC. Symp. Proc. 1992,271,621.
kharov, V. A. Catalysis by Supported Complexes;Elsevier: Amsterdam, (26) Cerveau. G.: Corriu. R. J. P.: Costa, N. J . " a - C r y s t . Solids
1981. 1993,163,226.
(21) Schubert, U. New. J . Chem. 1994,18,1049. (27) Morikawa, A,; Iyoku, Y.; Kakimoto, M.; Imai, Y. J . Muter.
(22) Allum, K. G.; Hancock, R. D.; Howell, I. V.; McKenzie, S.; Chem. 1992,2,679.
Pitkethly, R. C.; Robinson, P. J. J . Organomet. Chem. 1975,87,203. (28) Guizard, C.; Lacan, P. New J . Chem. 1994,18,1097.
(23) Panster, P.; Englisch, M.; Kleinschmit, P. DOS 3,404,702, 1984. (29) Arija, K.; Okahata, Y. J . A m . Chem. SOC.1989,111, 5618.
2014 Chem. Mater., Vol. 7, No. 11, 1995 Reviews

I
H,N' " \v/ 17 (n = 1-4) LJ 19
14 Figure 5. Compounds of the type (R0)3Sn-X-A.

compound was then metathesized with SnC14 to give

C13Sn(CHz),CH=CH2. Reaction of the C13Sn derivative
0 with tert-amyl alcohol in the presence of a base finally
resulted in the formation of The only other
C-N,
derivative of the general type (R0)3Sn-X-A is 19 (with
(CH,),SiMe(OEt),
chelating ethyleneglycolate substituents instead of mono-
15 dendate O R ) , internally coordinated by the y-amino
CH3(CHZ)17 0 group (Figure 5).34 This compound was obtained by
treating MezN(CH2)3SnPh3with glycol.
The other possibility to functionalize tin alkoxides
would be via functionalized chelating ligands, as dis-
cussed in the next section for metal alkoxides. Although
this appears to have the same potential as, for instance,
0 16 for the modification of Ti(OR')4 (vide infra), no com-
Figure 4. Selection of compounds 2 with other functional pounds of this type are currently known.
groups A than those in Figures 1-3. Metal Alkoxide Derivatives. There are interesting
potential applications for compounds 1 with E Si. *
strategy was developed slightly different from those However, only very few derivatives of this type are
previously discussed. To derivatize N,N-dioctadecyl- known, Le., the underlying basic chemistry is not yet
amine, the amine was first reacted with succinic anhy- developed. One of the reasons is that the functional
dride. N,N-Dioctadecylsuccinamic acid was obtained by group A cannot be linked to the alkoxide moiety by a
this reaction which provided a new coupling site for the hydrocarbon spacer as with silicon o r tin, due to the
later reaction with aminopropyltriethoxysilane. hydrolytic cleavage of the more polar E-C bonds.
Alkoxystannane Derivatives. The chemistry of Complexing ligands (CL) have often been reported in
alkoxystannanes is intermediate between that of the sol-gel literature as chemical additives to moderate
alkoxysilanes and alkoxides of typical metals, such as the reactivity of non-silicate metal alkoxides. Acetic
aluminum, the transition metals, or the lanthanides. A acid or acetylacetone were mainly used for this purpose.
catalyst is needed to accelerate the reaction of alkoxy- When non-silicon alkoxides are reacted with carboxylic
silanes with water. Tin alkoxides and metal alkoxides acids, P-diketones, P-ketoesters, o r related compounds
react much faster, and their hydrolysis and condensa- (CL-HI, part of the alkoxide groups is substituted by
tion reactions often must be slowed down by chemical carboxylate or P-diketonate groups, etc. (eq 7). A new
additives. On the other hand, silicon and tin have in molecular precursor E(OR),(CL), is obtained which
common that Si-C or Sn-C bonds, respectively, are not exhibits a different molecular structure and reactivity.
easily hydrolyzed. Therefore, compounds of the type Upon addition of water, the alkoxy groups and not the
(R0)3SnR can in principle be employed for the prepara- complexing ligands are primarily h y d r ~ l y z e d . ~ ~
tion of organically substituted stannates by sol-gel
processing. This was mainly demonstrated by Reuter E(OR),+, + xCL-H -.E(OR),(CL), + xROH (7)
et al.30 and Ribot et al.31 Nevertheless, compounds of
this type were only rarely used for sol-gel processing. However, complexing ligands can also be used for
This may be due to their low availability, which is organic functionalization. The most obvious choice are
particularly true for functionalized compounds of the functionalized carboxylic acids. Their reaction with
type (R0)3Sn-X-A. The trichlorostannyl compounds metal alkoxides provides the carboxylate derivatives
1732,33 (Figure 5) or HO(CHz),SnC13 ( p = 3-633) are (RO),E[OOC-X-A], where the functional group A is
interesting candidates, but the corresponding alkoxides linked via the carboxylate group and some spacer X to
are not yet known. The alkenyl compounds ( t A m 0 ) 3 - the metal alkoxide moiety. [Since the degree of associa-
Sn-X-CH=CHz (Am = amyl; X = (CH&, p = 2, 3; tion was not determined for most derivatives, mono-
C6H4) (IS) were prepared in a multistep procedure: meric formulas are given in this article. However, in
Reaction of CyaSnCl (obtained by metathesis from most cases dimerization or oligomerization is highly
Cy4Sn and SnC14; Cy = cyclohexyl) with the correspond- probable.] For instance, Ti(OEt)4 reacted with meth-
ing Grignard reagents gave Cy3Sn(CH&CH=CHz. This acrylic acid up to a maximum of 1.33 mol equiv.
Although the substitution products themselves were not
(30) Reuter, H.; Kremser, M.; Schroder, D.; Jansen, M. Muter. Res. isolated, their primary hydrolysis products, discussed
SOC.Symp. Proc. 1992,271,33. in the next section, showed the products to have the
(31) Ribot, F. 0.;Banse, F.; Sanchez, C. Muter. Res. SOC.Symp. Proc.
1992,271,45;1994,346,121.
(32) Hutton, R. E.; Oakes, V. Adu. Chem. SOC.1976, 157, 123. (34) Dakternieks, D.; Dyson, G.; Jurkschat, K.; Tozer, R.; Tiekink,
Nakahira, H.; Ryu, I.; Ikebe, M.; Oku, Y.; Ogawa, A,; Kambe, N.; E. R. T. J . Organomet. Chem. 1993,458,29.
Sonoda, N.; Murai, S. J . Org. Chem. 1992,57,17. (35) Leading references: Sanchez, C.; Livage, J.; Henry, M.; Ba-
(33) Jousseaume, B.; Lahcini, M.; Rascle, M.-C.: Ribot, F. 0.: bonneau, F. J . Non-Cryst. Solids 1988,100,65. Sanchez, C.;Livage,
Sanchez, C. Organometallics 1995,14,685 J. New J . Chem. 1990,14,513.
Reviews Chem. Mater., Vol. 7, No. 12, 1995 2015
,CH,-CO,R
HC
, = C,
C0,l i(OR),

H,C
-
=C \
CO,R

Figure 6. Reaction of Ti(0R')d with itaconic anhydride.

same constitution as those obtained in the reaction with

acetic acid. From the reaction of Zr(OPr"14 with meth-
acrylic acid both Zr(OPrn)3(0Mc)and Zr(OPrn)z(OMc)2
(OMc = methacrylate) were isolated.36 Other Zr(OR)3- / 23: OR = O-CH,CH=CHZ
(carboxylate) derivatives were similarly obtained by
reacting Zr(OPr)4 or Zr(OBut)4 with cinnamic acid or
sorbic acid.37 - \
The reactive double bonds in the (methlacrylate 0-R
derivatives are fully accessible for later polymerization Figure 7. Compounds of the type (R'0)zE-X-A (E = Ti, Zr).
reactions.36 The same is true, for instance, for the chloro The formulas of 20, 23, and 24 represent only the chemical
substituent, when chloroacetic acid is reacted with composition and the mode of linking the organic group but not
metal alkoxides. The following examples show that, in the structures of the compounds.
principle, the same strategies can be used to modify the
carboxylate derivatives (RO),E[OOC-X-A],, as for the Strengthening of a metal-ligand bond by its incor-
previously discussed organofunctional alkoxysilanes poration into a five-membered chelate system is also a
(R013Si-X-A (2, eqs 3 and 4). good strategy for carboxylic acids. For this reason
Phosphanyl-substituted metal alkoxides (RO)3E- a-hydroxy acids were used for the modification of metal
(OOC-X-PPh2) (E = Ti, Zr) were not obtained by direct a l k o ~ i d e s .a-Hydroxy
~~ acids having a second functional
reaction of the corresponding carboxylic acids with group a t a carbon atom more distant from the COOH
Ti(ORI4. However, addition of HPPh2 to the acrylic group are therefore very well suited for the preparation
double bond of (Pr0)3E(OOC-CH=CHz) (E = Ti, Zr) of organofunctional metal alkoxide derivatives of the
gave the phosphinopropionate derivatives (PrO)3E(OOC- type 1. Both methacrylamidosalicylicate modified Zr-
CHzCHzPPh2). The phosphinoacetate derivative (PrOIs- (OPr)441and 2,4-dihydroxybenzoate-modified Ti(oF'1-94~~
Zr(OOC-CHzPPh2) was prepared by the reaction of were used as sol-gel precursors. The former compound
(Pr0)3Zr(OOC-CH&l) with LiPPh2 similar to eq 3.38 contains a reactive double bond as the functional group
Another phosphanyl-substituted titanium alkoxide, A, suitable for polymerization reactions, while in the
( B U O ) ~ T ~ [ ~ - C ~ H ~ ( C Hwas ~ ) ~obtained
P P ~ ~ ] , from latter compound the second OH group is available for
L ~ [ C ~ H ~ ( C H Z ) and
~ P P(~BZ~ I0 1 3 T i C l . ~ ~ coupling reactions, etc.
If the reaction of metal alkoxides with carboxylic acids A recent study proved a-amino acids to be equally
is slow, esterification of the carboxylic acid by the suited. The X-ray structure analysis of [Ti(OEt)3-
liberated alcohol may become a competing reaction (vide (glycinate)]~ (21) showed that the a-amino group par-
infra). The same is true if the carboxylate ligand is not ticipates in binding the carboxylate ligand to the metal
tightly bound and a n alcohol is used as the solvent. The and improves stability of the carboxylate derivative by
water produced by esterification partially hydrolyses the formation of a five-membered chelate ring.43 Amino
remaining alkoxide groups. To overcome this potential acids with a second functional group a t one of the more
problem, Ti(OPr94 was reacted with itaconic anhydride distant carbon atoms therefore can also be used for the
(eq 8).39 Due to the unsymmetric substitution of the preparation of type 1 compounds. This was shown for
five-membered ring, two isomers were formed. Both Ti(OEt)3(ly~inate).~~ The uncoordinated amino group
contain a polymerizable double bond, although in a reacted with nickel salts as primary amines to give the
different position relative t o the Ti(OPr93 group. The complex (N~[NHZ(CH~)~CH(NH~)COOT~(OE~)~]~}~+ (the
reaction proceeds without the formation of a n alcohol precursor of 22).
(Figure 6). The chemical bond between P-diketonates and metal
The formation of a five- or six-membered metallacycle alkoxide moieties is inherently stronger than that of
results in considerable stabilization of the metal-ligand carboxylates. However, P-diketonates with functional
bond. For instance, compound 20 was prepared by substituents are less readily available. Two examples
reaction of Ti(OPri)4 with isoeugenol. Bonding of the containing polymerizable double bonds as functional
isoeugenolate ligand to the metal is much stronger than organic groups are shown in Figure 7 (23,442445). These
that of a simple alkoxy or aryloxy ligand. This is due
to chelation by the a-methoxy group. The OPr groups (40)Bradley, D. C.; Mehrotra, R. C.; Gaur, D. P. Metal Alkoxides;
of 20 were cleaved during base-catalyzed hydrolysis, Academic Press: London, 1978.
(41) French patents 91 11634 and 91 11635, cited in ref 45.
while one isoeugenolate ligand per two titanium atoms (42) Barglik-Chory, C.; Schubert, U. Proc. 1st Europ. Workshop on
was retained.39 Hybrid Organic-Inorganic Materials; Sanchez, C . , Ribot, F., Eds.; P a n s
1993, p 261. Barglik-Chory, C. Ph.D. Thesis, Universitat Wiirzburg,
1995.
(36) Schubert, U.; Arpac, E.; Glaubitt, W.; Helmerich, A,; Chau, C. (43) Schubert, U.; Tewinkel, S.; Moller, F. Inorg. Chem. 1995,34,
Chem. Muter. 1992, 4 , 291. 995.
(37) Buhler, H. Ph.D. Thesis, Universitat Wiirzburg, 1991. (44) Sanchez, C.; In, M.; Toledano, P.; Griesmar, P. Mater. Res. SOC.
(38) Buhler, H.; Schubert, U. Chem. Ber. 1993, 126, 405. Symp. Proc. 1992,271, 669. Chatry, M.; Henry, M.; In, M.; Sanchez,
(39) Barglik-Chory, C.; Schubert, U. J . Sol-Gel Sei. Technol., in C.; Livage, J. J. Sol-Gel Sci. Technol. 1994, 1, 233.
press. (45) Sanchez, C.; In, M. J . Non-Cryst. Solids 1992, 147, 148, 1.
2016 Chem. Mater., Vol. 7, No. 11, 1995 Reu ie w s

compounds were in situ prepared by reaction of allyl or There are only few applications where compounds of
methacryloxyethyl acetoacetate with an excess of Zr- the type 1 are processed alone. In most cases mixtures
(OPr)4 (Le., the reaction mixture probably consisted of of two or more different precursors are used. The
23 or 24 and unreacted Zr(0Pr)d. Allyl acetoacetate control of the homogeneity (or deliberate heterogeneity)
derivatives were similarly obtained with Ti(OBuh3jor of the chemical subunits is then another key issue.
A ~ ( O B U ” )Spectroscopic
~.~~ and structural data of the In this section we will focus on the questions arising
hydrolysis products of these mixtures (see next section) from the presence of organic functionalities. A compre-
showed the /3-diketonate to be coordinated as indicated hensive treatise on the hydrolysis and condensation
in Figure 7. reactions of organically modified alkoxides is not in-
Reaction of benzoylacetone (bzac-H) with A1(OBut)3, tended.
Zr(OR’)4,or Ti(OBut)4gave the P-diketonate derivatives Alkoxysilane Derivatives. Single Precursors. The
A1(OBuf)3-,(bzac),, Zr(OR)4,(bzac), ( p = 1,21, and Ti- influence of the steric and electronic properties of the
( OBut)2(bzac)2,respectively. Thermal reaction of some group R on the hydrolysis and condensation kinetics of
derivatives with Cr(C0)G gave metal complexes having organically substituted alkoxysilanes RSi(OR13 was
a Cr(C0)3 moiety iz-bonded to the phenyl group of the recently discussed in a review article.48 It can be
benzoylacetonate ligand; i.e., the phenyl substituent was implied that functional and nonfunctional groups R of
used as a “functional” group to coordinate metal complex comparable size and electronic properties have the same
fragments.47 influence, if the organic function A in 2 does not interact
with the silicon atom49or does not catalyze the reaction.
Primary Hydrolysis and Condensation This can be expected if the group A has either basic or
Processes acidic properties.
Aminoalkyl-substituted alkoxysilanes are an example
When water is added to metal alkoxides E(OR),, t o illustrate this point. Both internal coordination of
hydrolysis and condensation reactions are initiated, the amino group to the weakly Lewis acidic silicon atom
eventually leading to E-0-E groups and formation of and strong hydrogen bonds between the silanol groups
metal oxide structures. The parameters that influence of hydrolyzed (aminopropy1)trialkoxysilanes and the
the sol-gel process have been thoroughly studied NH2 group were debated.jO Due to these interactions,
mainly for Si(OR)4 but also for some non-silicon alkox- the rates of the uncatalyzed hydrolysis and condensa-
ides.l The water:alkoxide ratio, pH, temperature, con- tion reactions of (aminopropy1)trialkoxysilanesare simi-
centration of the reactants, and the kind of steric and lar to those of alkyltrialkoxysilanes in the presence of
electronic properties of the O R groups, to name only a base ~ a t a l y s t . j l -According
~~ to gel permeation chro-
some of the relevant parameters, influence not only the matographic (GPC) studies, the octameric species
kinetics of the hydrolysis and condensation reactions but [Et2N(CH2)3Si03/218were predominantly formed in the
also the nano- and microstructure of the obtained oxide. methanolic solution upon addition of water to Et2N(CH2)3-
When (organically) modified alkoxides (R‘O),-,ER, Si(OEt13. Dimerization of these species occurred to a n
are reacted instead of the parent alkoxides E(OR),, the appreciable amount without methanol, but no higher
sol-gel process is of course influenced by the non- oligomers were observed. A higher si1ane:water ratio
alkoxide ligands. The hydrolytically stable groups R resulted in a faster reaction but did not significantly
change the reactivity of the element E to which they influence the oligomer d i ~ t r i b u t i o n . ~ ~
are directly bonded, due to electronic and steric effects. The development of the molar mass distribution by
Since they reduce the number of alkoxide ligands, the GPC was also investigated for vinyltrimethoxysilane
degree of inorganic cross-linking in the gels formed by (VTMS),54GLYM0,55,56and MEM0.55,5i GPC and 29Si
the polycondensation reactions (i.e., the number of NMR investigation^^^,^^ of the HC1-catalyzed hydrolytic
E-0-E links per atom E) is necessarily reduced. A key polycondensation of VTMS in ethanol showed that
issue is the position and orientation of the organic increasing the H20:VTMS ratio increased the average
groups in the primary hydrolysis products, which con- degree of oligomerization ( n , maximum of n = 18 for
stitute the inorganic building blocks. Their structure H20:VTMS = 1.6) and the molecular weight distribu-
predetermines the microstructure of the final materials. tion. With a n increasing H20:VTMS ratio the percent-
When compounds of the type 1 with functional organic
groups are employed, additional questions arise: (48) Osterholtz, F. D.; Pohl, E. R. J . Adhesion Sci. Technol. 1992,
(i) How stable are the organic functions A and the 6,127.
E-X-A link during sol-gel processing? (49) Pohl, E. R.; Osterholtz, F. D. Polym. Prepr. 1983,24,200.
(50) Plueddemann, E. P. Silylated Surfaces; Leyden, D. E., Collins,
(ii) Do the organic functionalities interfere with the W. T., Eds.; Gordon & Breach: New York, 1980; p 31. Ishida, H.;
sol-gel chemistry of the precursors? Chiang, C.; Koenig, J. L. Polymer 1982,23,251. Ishida, H.; Naviroj,
S.; Tripathy, S. K.; Fitzgerald, J. J.; Koenig, J. L. J . Polym. Sci. 1982,
(iii) How does the incorporation of organic function- 20, 701. Vrancken, K. C.; van der Voort, P.; Gillis-D’Hamers, I.;
alities, many of them being quite bulky, influence the Vansant, E. F. J . Chem. SOC.,Faraday Trans. 1992,88, 3197.
build-up and the properties of the gel network? (51) De Zea Bermudez, V.; Armand, M.; Poinsignon, C.; Abello, L.;
Sanchez, J.-Y. Electrochim. Acta 1992,37,1603.
(iv) How is the function of the organic groups (their (52) Cao, W.; Hunt, A. J. Muter. Res. SOC.Symp. Proc. 1994,346,
optical properties or their catalytic activity, for instance) 631.
(53) Piana, K.; Schubert, U. Chem. Mater., in press.
influenced by the oxide matrix in which they are (54) Abe, Y.; Taguchi, K.; Hatano, H.; Takahiro, G.; Nagao, Y.;
incorporated? Misono, T. J . Sol-Gel Sci. Technol. 1994,2 , 131.
( 5 5 ) Piana, K.; Schubert, U. Chem. Mater. 1994,6 , 1504.
(56) Grey, J. P. Adhesion (LondonJ 1988,12,106.
(46) Hoebbel, D.; Reinert, T.; Endres, K.; Schmidt, H. Proc. 1st (57) Miller, J. D.; Hoh, K.-P.; Ishida, H . Polym. Compos. 1984,5,
Europ. Workshop on Hybrid Organic-Inorganic Materials; Sanchez, C., 18.
Ribot, F., Eds.; P a n s , 1993; p 319. (58) Devreux, F.; Boilot, J. P.; Chaput, F.: Lecomte, A. Muter Res.
(47) Schubert, U.; Buhler, H.; Hirle, B. Chem. Ber. 1992,125,999. SOC.Symp. Proc. 1990,180, 211.
Reviews Chem. Mater., Vol. 7, No. 11, 1995 2017
age of Vi(Me0)zSiO- units decreased, while the per- p ~ l y m e r i z a t i o n . Since
~ ~ a catalyst has to be used for
centage of ViSi(O-)s units increased. The spinnability sol-gel processing, its influence on the epoxy group is
of the sols was related to the ratio of the different crucial. Complete hydrolytic opening of the epoxide ring
structural ~ n i t s . 5 ~ within 17 h was observed a t low pH with HC104, H2S04,
The uncatalyzed hydrolysis of both GLYMO and or H3PO4 as the catalyst. At pH 5.5 (HzCO31, ring
MEMO resulted in the slow formation of rather small opening was negligible even if a n excess of water was
oligomer^.^^,^^ The degree of oligomerization was also employed.65 In the presence of 0.1 equiv of l-methyl-
influenced by the si1ane:water ratio. 1-Methylimidazol imidazol, i.e., under basic conditions, and a n excess of
as the catalyst accelerated the formation of oligomers water the epoxide concentration decreased slowly. Gly-
(with n = 8 and 16) from GLYM0.55 Acid-catalyzed col and epoxide analyses after one day showed about
reaction resulted in the formation of a mixture of 15% of the epoxide groups converted to the glycol, and
oligomers, a significant portion being the cyclic tetra- about 50% after 7 days a t 25 "C. However, the rate of
m e r ~ . ~ ~ the epoxide hydrolysis reaction was slow compared with
According to the GPC investigations, the growth of the siloxane polycondensation reaction. The different
oligomers from MEMO strongly depends on the used reaction rates allow the preparation of hybrid materials
catalyst. With 1-methylimidazol, methacrylic acid, or by a two-step process, in which formation of the Si-
Zr(OPr")Z(OMc)zas catalysts condensation essentially 0-Si network is carried out first and later the epoxy
stopped a t the stage of medium-sized oligomers ( M p < polymerization is i n d ~ c e d . ~ ~ , ~ ~
lo4). Only with the strongly basic (dimethylamino)- Precursor Mixtures. One of the basic ideas behind the
ethanol or with H F a s the catalysts larger polymers development of inorganic-organic hybrid materials by
were formed. In the (dimethy1amino)ethanol-catalyzed sol-gel processing is the blending of materials proper-
reaction the polymer growth was not finished after 3 ties by using mixtures of different precursors. In the
month^.^^,^^ According to another GPC and FTIR study, early days of this chemistry it was more or less
both the configuration and the molecular weight distri- implicitly assumed that in multicomponent precursor
bution of the polymers obtained from MEMO are de- systems there is a statistical distribution of the molec-
pendent on the solution pH. Below pH 4, a beaded ular building blocks in the final materials. However,
chain structure of cubical octamers or polycyclic caged considering the steric and electronic influence of differ-
blocks was obtained, while in neutral or basic environ- ent organic groups R on the hydrolysis and condensation
ments a double ladder structure was formed.57 A lH rates of RSi(OR)3, it is obvious that this will rather be
and 29SiNMR spectroscopic analysis of the hydrolysis the exception than the rule. This is not necessarily a
and condensation process of MEMO a t pH = 2 with a disadvantage. In the contrary, the deliberate engineer-
stoichiometric amount of water showed that hydrolysis ing of some nanoheterogeneity provides additional pos-
of the SiOMe groups is fast, but not complete.61 The sibilities for materials developments. However, this
composition of the sol reached a stationary state after requires the thorough investigation of the chemical
4 days. The larger percentage of R(MeO)Si(O-)Z units behavior and mutual influence of the precursors in
(60%)in this state is consistent with mainly linear or multicomponent sol-gel systems.
cyclic species in the aged sols. The number of RSi(0)3 A recent example to illustrate this point is the
(20%) units allowed a n estimate of the upper limit of development of inorganic-organic hybrid aerogels from
10 for the chain length. The difficulty of three- RSi(OMe)dSi(OMe)4 mixtures (R = terminal alkyl and
dimensional polycondensation was attributed to the size aryl or functional organic groups, such as 3-methacryl-
of the organic groups. Similar 29SiNMR spectroscopic oxypropyl or 3-gly~idoxypropyl).~ It was shown that
results were also reported by another group.62 under basic conditions the built up of the gel network
The results on the molecular mass distribution in is a two-step process. In the first stage, SiO,(OH),-
hydrolyzed alkoxysilanes 2 can be summarized a s (OMe), clusters are formed by hydrolysis and condensa-
follows. The growth mechanism of the siloxane oligo- tion of Si(OMe)4, while RSi(OMe13 basically is a cosol-
mers is probably the same as proposed by Brown for vent. In the later stage of the reaction the RSiE units
the condensation of cyclohexyl- or p h e n y l ~ i l a n e t r i o l . ~ ~ condense a t the surface of the primary clusters. The
Condensation of the functionalized silanes stops a t the fate of the individual alkoxides was conveniently moni-
stage of rather small oligomers unless very active tored by micro-Raman spectroscopy, which provided
catalysts are used. This is probably due to steric effects clear evidence for the two-step m e ~ h a n i s m . ~ ~
of the rather bulky organic groups. A structure in which organofunctional groups are
A major concern is the fate of the functional organic located a t the outside of the polysiloxane building
group A during sol-gel processing, particularly if they blocks, was also postulated from a 29Si and 31Psolid-
are not totally inert toward water. Although this is a state NMR study of a gel obtained from (Me0)SSi-
very critical issue, there are only few systematic inves- (CHz)sP(PhI(CHz)zOMeand Si(OEt)4 (1:2).68
tigations, most of them for GLYMO. The epoxy group In a mixture of two alkoxide precursors a mutual
in GLYMO is capable of forming either diol units by influence on the hydrolysis and condensation processes
hydrolytic ring opening or polyethylene oxide chains by
(64) Philipp, G.; Schmidt, H. J . Non-Cryst. Solids 1986, 82, 31.
(59) Nass, R.; Arpac, E.; Glaubitt, W.; Schmidt, H. J . Non-Cryst. (65) Schmidt, H.; Seiferling, B. Muter. Res. SOC.Symp. Proc. 1986,
Solids 1990.
~~ ~ -~~ 121. 370.
~,---,
~
73, 739.
(60) Greiwe, K.; Glaubitt, W.; Amberg-Schwab, S.;Piana, K. Muter. ( 6 6 ) Amberg-Schwab, S.; Arpac, E.; Glaubitt, W.; Rose, K.; Schott-
Res. SOC.Symp. Proc. 1992, 271, 725. ner, G.; Schubert, U. High Performance Films and Coatings; Vincen-
(61) Delattre, L.; Dupuy, C.; Babonneau, F. J . Sol-Gel Sci. Technol. zini, P., Ed.; Elsevier: Amsterdam, 11191;p 203.
1994, 2 , 185. (67) Homer, S.; Schwertfeger, F.; Hiising, N.; Schubert, U.; Kiefer,
( 6 2 ) Krug, H.; Schmidt, H. New J . Chem. 1994, 18, 1125. W. J . Non-Cryst. Solids, submitted.
( 6 3 ) Brown, J. F.; Vogt, L. H. J . Am. Chem. SOC.1965, 87, 4313. (68) Lindner, E.; Bader, A.; Mayer, H. A. Inorg. Chem. 1991, 30,
Brown, J. F. J . Am. Chem. SOC.1965, 87, 4317. 3783.
2018 Chem. Mater., Vol. 7, No. 11, 1995 Reviews
can be expected. For the MEMO/Si(OEt)4 system this
was studied by measuring the gel times (t~3).~’The
addition of MEMO to an acidic mixture of Si(OEt)4,
ethanol and water resulted in a considerable increase
of tG. Under basic conditions the increase of t G was less
dramatic. The influence of MEMO cannot only be
attributed to the effective decrease of the water con-
centration because of the faster hydrolysis of MEMO
in acidic environment compared to Si(OEt)4. It is rather
due to the incorporation of the methacryloxypropylsilyl
units in the gel network, which strongly influence the
cross-linking by polycondensation due to steric hin-
drance of the methacrylate group (vide supra) and the
smaller number of hydrolyzable OR’ groups.
Micro-Raman spectroscopy shed light on the funda-
mental chemical processes in another system composed
of two precursor silanes. There are three competing
reactions in the GLYM0/3-(aminopropyl)triethoxy-
silane/H20 system: ring opening of the epoxy group to
give a diol, formation of polyethylene units by poly-
merization, and reaction of both silanes to give /?-amino
alcohol links. Raman spectroscopy showed that the
latter reaction is d ~ m i n a t i n g . ~ ~
The pH, the concentration of F- (as the catalyst) and
the silane ratio was optimized by light scattering to
improve the clarity and structural homogeneity of gels
from Si(OEt)d(MeO)3Si(CH&NHCH2CH2NH2 or (Et0)3-
Si(CH&NH2 mixtures.52
Analysis of the chemical processes in systems with
two different alkoxide precursors and their relation to
the nanoscopic structure of the derived materials is
already very difficult. With more precursors this task
becomes even more complicated. In the present time,
a n optimization of such multicomponent sol-gel proc-
esses is only empirically possible because the h n d a -
mentals for a more rational proceeding are still lacking.
An example for such an optimization procedure in a
ternary system is the preparation of spheres of 0.2-1.5
mm in diameter from the three-component system
Si(OEt)d(MeO)3SiMd(MeO)3Si(CH2)3NH(CH2)2NH2 or
(Me0)3Si(CH2)3NH2.71
Alkoxystannane Derivatives. The sol-gel chemistry
of tin alkoxides is only little developed, compared with
silicon alkoxides. Structural information on the hy-
drolysis products of tin alkoxide derivatives (AmtO)3-
SnR with R = n-butyl, n-butenyl, or p - ~ t y r y lwas ~~
obtained by l19Sn NMR. In each case tin expands its
coordination from 4 in the monomeric precursors to 5 Zr (hcplocoordinotcd) @ 0 (ow b r i d p o 0 ~(propoxo)

and 6 in the hydrolysis products. Incomplete hydrolysis Zr (hancoordinrlcd) @ 0 (nIIyIaccluarCI;iIr.) 0 0 (hgdruxo bridges)

yielded tin oxo hydroxo clusters. The cluster

[(BuSn)12014(OH)sl2+was identified by X-ray structure O C

analysis (Figure 8). According to the l19Sn NMR Figure 8. Structures of the primary hydrolysis products
spectrum, the butenyl derivative has the same struc- [(B~Sn)12014(OH)6]~+31 (top) (only the first carbon of the butyl
ture. The cagelike cluster is surrounded by the organic group is drawn), %304(OR’)~(OMc)a,3~ (middle) and Zr10O6-
groups, and none of the organic groups R was cleaved (OH)4(0Pr)l~(allylacetoace~te)6~~ (bottom). Reprinted by per-
mission of the Materials Research Society and Kluwer Aca-
during hydrolysis. The covalent bond between tin and demic.
carbon allows the formation of inorganic-organic hybrid
materials, with the oxo cluster as a nanosized building block. One should bear in mind (also in the following
section on metal alkoxide derivatives) that the crystal-
(69) Van Bommel, M.J.; Ten Wolde, P. M. C.; Bernards, T. N. M. line compounds are only models for the structural units
J. Sol-Gel Sci. Technol. 1994,2, 167. in (amorphous!) gels.
(70) Posset, U.; Lankers, M.; Kiefer, W.; Steins,H.; Schottner, G.
Appl. Spectrosc. 1993, 47, 1600. Theobald, S.; Posset, U.; Lankers, As mentioned before, tin alkoxide carboxylates de-
M.; Kiefer, W.; Muller, M. M.; Schottner, G. J . Non-Cryst. Solids, rived from hnctional carboxylic acids are a still unex-
submitted.
(71) Yacoub-George,E.; Bratz, E.; Tilbcher, H. J. Non-Cryst. Solids plored possibility to anchor functional groups to a
1994,167,9. stannoxane network. Succinic acid reacts with Sn-
Reviews Chem. Mater., Vol. 7, No. 11, 1995 2019

(OBut)4in a 1:l ratio by substitution of two equivalents or Zr4O(OPr)lo(acac)4,the primary hydrolysis product
of butanol and formation of a tin alkoxide derivative of [Zr(OPr)a(aca~)12.~~ A smaller metal$-diketone ratio
with a chelating succinate ligand. Upon hydrolysis of results in the formation of larger clusters. The decamer-
(BufO)2Sn(00CCH2CH2COO) at neutral pH with an ic cluster Zr~~0~(OH)~(OPr)~~(allylacetoacetate)~ (Figure
excess of water the succinate ligand was retained. Its 8) carrying functional organic ligands, was obtained
cleavage was achieved only when 70% nitric acid was from hydrolysis of a solution of Zr(OPr)4 and 0.6 equiv
added to a suspension of the hydrolysis product of allyl a c e t ~ a c e t o n e . ~ ~
Sn0(00CCH2CH2C00).72Although this behavior may Hydrolysis experiments of methacryloxyethyl aceto-
not be typical for simple carboxylic acids, it a t least acetate modified Zr(OPr)4 (24) (Figure 7) with different
shows that the tin-carboxylate bond can be stabilized Zr:P-diketonate ratios showed that this is the key
by chelation, as previously discussed for metal alkoxide parameter that controls the structure and texture of the
carboxylates. derived organic-inorganic hybrid materials. A careful
Metal Alkoxide Derivatives. There are a few X-ray adjustment of this ratio led to zirconium oxo species
structure analyses of oxo clusters modified by organo- with more or less open structure^.^^
functional chelating ligands. They show that the nature These and related examples can be generalized as
and the structure of the primary hydrolysis products, follows:44
as in silicon chemistry, is the same with functional or (i) In all examples where the primary hydrolysis
the corresponding nonfunctional organic ligands. Al- products were identified, the P-diketonate ligands were
though these results were obtained from crystalline completely retained during hydrolysis, i.e., the metal-
materials, it can be assumed that they also apply to the diketonate bond is rather hydrolytically stable. How-
amorphous state. ever, there is one report that part of the allyl aceto-
The primary hydrolysis products Ti&( OR')8(0Ac)s acetate ligands was lost during hydrolysis of Zr- and
were obtained by partial hydrolysis of acetic acid modi- Al-alkoxide derivative^.^^
fied Ti(OR')4( R = Et, Bun, Pr2).73The structurally same (ii) The P-diketonate ligands cover the oxo clusters
type of compound was isolated from the reaction of formed during hydrolysis. They are terminating ligands
Ti(OEt14 with methacrylic acid (Figure The car- preventing further condensation. The size of the oxo
boxylate groups in each compound are exclusively in a clusters can therefore be tailored by the metal$-
bridging mode. This places the methacrylate units at diketone ratio.
the outside of the cluster and makes them fully acces- (iii) The P-diketone ligands can additionally be used
sible for later chemical reactions. Hydrolysis of the to carry an organic functionality.
bismethacrylate compound Zr(OPrn)2(0Mc)2gave ZrO- Another approach for the preparation of organofunc-
( O M C ) ~a, polymeric compound already known with tional capped metal oxide clusters is the organic modi-
other carboxylate ligands. The monomethacrylate fication of preformed oxo clusters or colloids. The
Zr(OPrn)s(OMc)only reacted with 1.33 equiv of water principle was very impressively demonstrated by Ju-
to yield a compound of the composition ZrsOs(OH)- deinstein, who prepared organically modified polyoxo-
(OPrn)2(OMc)swith an unknown structure.36 tungstates of the composition [W11Si03&3205R2)1~-by
In these examples, the meta1:methacrylate ratio was reaction of organofunctional alkoxy- or chlorosilanes
retained during hydrolysis. However, simple carboxyl- RS& ( R = vinyl, allyl, 3-methacryloxypropyl or styryl)
ates are rather weak ligands and are largely removed with &[WllSiO391 .78
upon extended h y d r ~ l y s i s .A~ large
~ amount of organic
groups is then lost. This situation is considerably Materials Syntheses
improved by using a-hydroxy or a-amino a ~ i d s . If ~ ~ , ~ ~In this section representative materials will be dis-
a permanent organic modification of metal oxides is cussed, which have been developed by sol-gel process-
intended, Le., if the carboxylates are not just used to ing of organofunctional metal alkoxides as precursors.
control the reactivity of the alkoxides or the morphology There are already so many examples in the scientific
of the derived oxides, the use of such acids is strongly and patent literature that it is impossible to discuss or
adviced (see precursors sections). even mention all of them. We rather focus on some
Localization of the (functional) organic groups at the general aspects of preparation and the scope of currently
periphery of oxo clusters is also a common feature of feasible applications.
the hydrolysis products of /3-diketonate-modified metal 1. Inorganic-Organic Hybrid Polymers. Inor-
alkoxides. Structurally characterized examples are ganic-organic hybrid polymers, mostly used as coatings
Til8022(0Bu)~6(acac)~ (acac = acetylacetonate), formed for different purposes but recently also as bulk materi-
by partial hydrolysis of a solution of Ti(OBun)4in the als, constitute the technically most advanced type of
presence of 0.1 mol equiv of acet~lacetone,~5 Ce604(OH)4- applications in this field. They consist of a dual polymer
(acacllz, the hydrolysis product of [Ce(OPrl)z(a~ac)212,~~ network, in which cluster- or polymer-type inorganic
structures are linked by organic groups or polymer
(72) Roger, C.; Hampden-Smith, M. J.; Brinker, C. J. Mater. Res. fragments. Such materials combine to some extent the
SOC.Symp. Proc. 1992,271, 51. properties of organic polymers with those of metal
(73) Gautier-Luneau, I.; Mosset, A,; Galy, J. 2.Kristallogr. 1987, oxides.
180, 83. Larbot, A,; Laaziz, I.; Guizard, C.; Cot, L. Precursors
moleculaires de materiaux inorganiques 93; Le Grande Motte, 1989; Excluding materials in which the organic and inor-
Vol. 2, p 269. ganic polymer units are not covalently bonded together
(74) Doeuff, S.; Henry, M.; Sanchez, C.; Livage, J. J . Non-Cryst.
Solids 1987,89,206.
(75) Toledano, P.; In, M.; Sanchez, C. C. R. Acad. Sei. Paris Ser. 2 (77) Toledano, P.; In, M.; Sanchez, C. C. R. Acad. Sei. Paris Ser. 2
1991,313, 1247. 1990,311, 1161.
(76) Toledano, P.; In, M.; Sanchez, C. C. R. Acad. Sei. Paris Ser. 2 (78) Judeinstein, P. Chem. Mater. 1992,4,4; J . Sol-Gel Sci. Technol.
1990,311, 1315. 1994,2, 147.
2020 Chem. Mater., Vol. 7, No. 11, 1995 Reviews

Scheme 1. Sketch of the Different Possibilities of the kind and connectivity of both the organic and
Preparing Organic-Inorganic Hybrid Polymers inorganic building blocks can be varied (including
from Organofunctional Alkoxides" combinations of different groupings in both parts), but
EIORL also their ratio.
The following selected examples shall illustrate the
potential of the different approaches and options for the
sol-gel synthesis of hybrid polymers.
(R'O),E-terminated organic (macro)molecules [(R'O),.
E/,Y as Precursors. The nature and dimensionality of
lROI,E-A
the organic groupings Y linking the (RO),E groups can
be quite different. It can range from short links (for
example, very interesting microporous, high-surface-
area materials were made from alkenyl-, alkinyl-,
arylene-, or oligo(ary1ene)-bridged alkoxysilanes with
different structural features of the group Y79,80)to
shorter or longer organic macromolecules. Hybrid
polymers with highly branched organic cores were
A A
recently prepared by sol-gel processing of dendritic
0 The circles represent t h e inorganic substructure (which can
organo(alkoxy)silanes.81Non-silicate hybrid polymers
be cluster- or polymer-like), t h e sinuous lines t h e organic sub- have rarely been prepared by this route. As mentioned
structure. The connectivity is arbitraryly drawn. in the Introduction, this approach to the synthesis of
organic-inorganic hybrid polymers was recently
(see Introduction), there are three principal approaches reviewed2a,band will therefore not be further discussed
and several options to prepare inorganic-organic hybrid here.
polymers from organofunctional alkoxide precursors and Organofunctional Inorganic Clusters as Precursors.
related compounds (Scheme 1). Molecular oxo clusters of various sizes are available for
(i) Formation of the hybrid polymers from compounds many elements. However, their modification by organo-
of the type [(RO),E],Y, in which Y is an organic group functional groups is not trivial. Therefore, only few
or a macromolecule linking two (x = 2) or more (x > 2) materials have been prepared by this route. Although
E(OR), units. The structure of the preformed organic metal alkoxides are not necessarily involved, some
building blocks Y is retained in the final material. The aspects will nevertheless be discussed because of their
organic substructures are cross-linked by hydrolysis and relevance to sol-gel chemistry. Since the inorganic
condensation of the E(OR), units and, optionally, added building blocks formed during sol-gel processing of
E(OR),, i.e., by formation of the inorganic network. metal alkoxides often (depending on the reaction condi-
(ii) Formation of the hybrid polymers from function- tions) are like oxide clusters or colloidal oxide particles,
alized inorganic building blocks (oxo clusters or colloidal the chemistry of defined clusters with organofunctional
particles). The inorganic structures are cross-linked by groups models the situation during sol-gel processing
reactions of the organic functions. of the bifunctional molecular precursors 1 (Scheme 1).
(iii) Formation of the hybrid polymers from the One of the best defined type of clusters in silicon
bifunctional molecular precursors (RO),E-X-A (1) chemistry is that of the octameric spherosilicates
bearing a n inorganic ((RO),E) and a n organic function- (ROSiOa/& or silsesquioxanes (RSi03&. They have a
ality (A). The latter must be capable of undergoing ("double four ring") structure with the silicon atoms
polymerization reactions (see Figure 1 for some ex- being located a t the corners of a cube and the groups
amples). In the vast majority of examples these precur- OR or R sticking out of the cluster. Clusters with
sors are first reacted with water, and after sol-gel proc- various groups OR o r R have been s y n t h e s i ~ e dand
~~.~~
essing, the organic groups A attached to the inorganic allow the deliberate preparation of hybrid polymers with
building blocks are polymerized or cross-linked to form very defined structure^.^^ The cubic silsesquioxanes are
the organic network. Although the order of forming structurally related to the oligomeric intermediates
both networks is the same a s in the second approach, formed during sol-gel processing of the alkoxysilanes
there is a procedural difference, a s the inorganic build- 2 (see Hydrolysis and Condensation section). The
ing blocks are formed only in situ. organic cross-linking of the octameric species models,
There are several options for all approaches by which in some way, the synthesis of hybrid polymers starting
the composition, structure and properties of the materi- from (R0)3Si-X-A (2).
als can be varied: Coupling between the (ROSiO& building blocks was,
(i) Cocondensation of several alkoxides (either binary for instance, done for R = SiMe2H by hydrosilylation
alkoxides, E(OR),, o r different organically or organo-
functionally substituted alkoxides); alkoxides of differ- (79) Leading references: Shea, K. J.;Webster, 0.;Loy, D. A. Muter.
ent elements can be combined. Res. SOC.Symp. Proc. 1990,180,975. Shea, K. J.;Loy, D. A,; Webster,
(ii)Organic copolymerization with organic monomers, 0. J . Am. Chem. Soc. 1992, 114, 6700. Oviatt, H. W.; Shea, K. J.;
Small, J. H. Chem. Muter. 1993, 5, 943.
macromolecules, o r a reactive substituent originating (80) Corriu, R. J. P.; Moreau, J. J. E.; Thepot, P.; Wong Chi Man,
from another organofunctional alkoxide. M. Chem. Muter. 1992, 4 , 1217. Corriu, R. J. P.; Moreau, J.J. E.;
Thepot. P.; Wong Chi Man, M.; Chorro, C.; Lere-Porte, J.-P.;Sauvajol,
(iii) Choice of thermal or photochemical polymeriza- J.-L. Chem. Muter. 1994, 6 , 640.
tion. (811 Michalczyk, AI., personal communication.
With these options, there are many possibilities to (82) Dittmar, U.; Hendan, B. J.; Florke, E.; Marsmann, H. C. J .
Organomet. Chem. 1995,489, 185.
chemically modify organic-inorganic hybrid polymers (83) Hoebbel, D.; Endres, K.; Reinert, T.:Schmidt, H. Muter. Res.
and thus to tailor their macroscopic properties. Not only SOC.S y m p . Proc. 1994, 346. 863.
Reviews Chem. Mater., Vol. 7, No. 11, 1995 2021

with vinyl-substituted siloxaness5 or, vice versa, for R network develops to which the functional organic groups
= SiMeZCH=CH2 by hydrosilylation with hydrogeno- are attached. While gelation occurs, the materials can
siloxanes.85@ Microporous, hydrophobic hybrid poly- be moulded or applied a s coatings with conventional
mers with a n ordered silicate substructure were ob- coating techniques (spray, dip, spin-on coating, etc.).
tained by direct coupling of vinyl- and hydrogeno- Following the sol-gel step, the organic groups are
terminated spherosiloxane unitses6 The chain length thermally or photochemically polymerized or crosslinked
connecting the spherosiloxane units was found to be to form the organic network. This results in a perma-
very critical with regard to the porosity of the hybrid nent hardening of the materials. Whether thermal o r
material. Porous materials were obtained only with photochemical curing is more suitable depends on the
0-Si-C-C-Si-0 links, while shorter or longer links chemical system and the kind of application. Photo-
resulted in materials with low surface area^.^^,^^ Re- chemical curing is preferred for coatings of polymers
cently, heterocoupling between the siloxane clusters with low thermal stability or for applications in which
with R = SiMesH and allyl acetoacetate-modified alu- very rapid curing is essential.
minum and zirconium alkoxides was also r e p ~ r t e d . ~ ~ , ~For ~ example, a highly flexible, nevertheless abrasion
Hybrid polymers with tin oxide clusters as the inor- resistant coating for polyethyleneterephthalate or poly-
ganic building block were obtained by AIBN promoted carbonate was obtained from GLYMO, with l-methyl-
organic polymerization of the butenyl groups of [(bu- imidazol as the catalyst. 1-Methylimidazol acts a s a
tenyl-Sn)1~014(0H)61~~.~~ Quasi-elastic light scattering sol-gel catalyst a t room temperature, and in the second
indicated that the hydrodynamic diameter of the par- step of the materials synthesis as a n initiator for the
ticles increased from 1 to 6 nm by the polymerization. epoxide polymerization a t a higher
The small size of the organically cross-linked particles Due to the different reaction modes of the epoxide group
was attributed to the low reactivity of the butenyl (vide supra) sol-gel processing of GLYMO can, of
groups. In another strategy [(BuSn)12014(0H)612'clus- course, also be run in a way to deliberately produce diol
ters were transformed to hybrid polymers by cross- units. Antifogging coatings on glass were developed by
linking with dicarboxylic acids, such as adipic, dodec- this approach.g0
anoic, or terephthalic acid.87 However, only a few materials developments are
The organic functions of the organofunctional poly- based on a single precursor because precursor mixtures
oxotungstates [WllSi03j(Si205Rz)14- ( R = vinyl, allyl, usually allow a better tailoring of the materials proper-
3-methacryloxypropyl, or styryl) were polymerized in ties. To avoid the potential problems associated with
the presence of a radical initiator. The optical and precursor mixtures (see Hydrolysis and Condensation
electrochemical properties of the polyoxotungstates were section), the acrylate-substituted alkoxysilanes 3 and
not changed by the organic cross-linking. Therefore, the 4 (Figure 1) and related compounds were developed.
transparent thin films obtained on different kind of Although they are single precursors, the macroscopic
substrates turned blue on W irradiation or electro- properties of the derived hybrid materials can easily be
chemical r e d u ~ t i o n . ' ~ modulated by varying the structure of the organic spacer
The polymerization of oxide (colloid)particles surface- between the (methlacrylate group(s1 and the (R013Si
capped with functional organic groups is a very promis- group, as well as the number of (methlacrylate groups
ing but virtually unexplored strategy for the preparation available for polymerization (i.e., the degree of organic
of organic-inorganic hybrid polymers. For instance, cross-linking).6-8 The Young's modulus of the photo-
hybrid polymers with titanate building blocks were chemical cross-linked materials was adjustable between
obtained by prehydrolysis of Ti(OBu)4with only 1equiv less than 1 and 4000 MPa, and the thermal expansion
of water (presumably forming titanate clusters or oli- coefficient between 50 x K-l and more than 250
gomers), followed by complexation with unsaturated x K-l, just by varying the organic structures.8
organic acids, such as cinnamic acid. Copolymerization Some other advantages of these hybrid polymers, such
with styrene was then performed to give transparent as low shrinkage, high flexural strength, and the low
brown, water-stable polymems8 Core-shell materials water adsorption, led to their application as dental
with a titania core and a polymer shell were made by filling materials (combined with some inorganic fillers).s
grafting Ti(OPrc)2(0OC-C17H35)(methacrylate) to the The refractive index is another physical parameter that
surface of submicron Ti02 particles, followed by emul- was varied by modification of the organic structures of
sion polymerization with methyl m e t h a ~ r y l a t e . ~ ~ the precursors. Lenses made from the acrylate(a1koxy)-
Hybrid Polymers from Single-Component Alkoxide silanes a s precursors had comparable optical properties
Precursors. Inorganic-organic hybrid polymers are and densities than those made from purely organic
prepared from organofunctional alkoxides (RO),E-X-A polymers. However, their abrasion resistance was
(1, see Figure 1 for some suitable examples) in a two- distinctly better.7 The materials made from these
step procedure. During sol-gel processing the inorganic single-precursor silanes very impressively illustrate that
tailoring of materials properties is possible by tailoring
the organic and inorganic building blocks.
(84)Agaskar, P. A. J.Am. Chem. SOC.1989,111, 6858.
(85) Hoebbel, D.; Pitsch, I.; Heidemann, D.; Jancke, H.; Hiller, W. Only few non-silicate materials were synthesized from
Z . Anorg. Allg. Chem. 1990, 583, 133. Hoebbel, D.; Pitsch, I.; organofunctional single-component alkoxides. One ex-
Heidemann, D. 2. Anorg. AZlg. Chem. 1991,592,207.
(86) Hoebbel, D.; Endres, K.; Reinert, T.; Pitsch, I. J . Non-Cryst. ample is the preparation of photochromic coatings from
Solids 1994,176, 179. (BunO)3Ti(allyla ~ e t o a c e t a t e ) . ~ ~
(87) Ribot, F.; Banse, F.; Diter, F.; Sanchez, C. New J . Chem., in
press. Co-Condensation of Organofunctional Alkoxides with
(88) Suvorov, A. L.; Spasskii, S. S. Proc. Acad. Sei. USSR 1959, Binary Alkoxides. The general idea behind the prepa-
127, 615.
(89) Caris, C. H. M.; van Elven, L. P. M.; van Herk, A. M.; German,
A. L. Brit. Polym. J . 1989,21, 133. (90) Kasemann, R.; Schmidt, H. New J . Chem. 1994,18, 1117.
2022 Chem. Mater., Vol. 7, No. 11, 1995 Reviews

ration of inorganic-organic hybrid polymers from or-

ganofunctional alkoxides 1 is the notion of getting
materials with properties between those of purely
organic polymers and purely inorganic materials. A
steady change of materials properties between the two
extremes is possible only if the ratio between the organic
and inorganic building blocks is adjustable. The inor-
ganic portion in the final materials can be increased by
co-condensation of the organofunctional alkoxides 1 with
binary alkoxides E(OR1,. Employing alkoxides of dif-
ferent elements E additionally allows some variation of
the chemical nature of the inorganic building blocks and
of the materials properties originating from them.
The first commercial application of inorganic-organic
hybrid polymers may illustrate this point. A scratch-
resistant, transparent hard coating for polycarbonate
lenses was developed from mixtures of GLYMO,
Si(OMe14, and E(OR), (E(OR), = Ti(OEt)4, Zr(0P1-14,
or A(OR)3, r e s p e ~ t i v e l y ) .The
~ ~ binary alkoxides have
two functions: they build up the inorganic substructure
of the final material, and the non-silicon alkoxides
E(OR), already a t room temperature catalyze the
polymerization of the epoxide groups. Zr(OPr)4 is a
more effective catalyst than Ti(OEt)4.64 A prepolymer
of low viscosity was first obtained by very slow addition
of to 3/16of the stoichiometric amount of water and
HC1 a s the catalyst to the mixture of alkoxides. In the
prepolymer the alkoxide moieties were partially hydro-
lyzed and condensed, and partial polymerization of the
expoxide groups had taken place. After addition of the
rest of water and, optionally, dilution with butanol, the
mixtures were applied to the plastic lenses by the spin-
on coating technique. The coatings were then thermally
cured.g1 The viscosity of the prepolymers increased
steadily, mainly because of progressive polymerization
of the epoxide groups.64 Coating is possible only within
a certain viscosity range. Since the ratio of the alkox-
Figure 9. Cartoon of hybrid organic-inorganic polymers
ides in the GLYMO/Si(OMe)djE(OR), mixtures influ- obtained from methacryloxyethyl acetoacetate modified Zr-
ences both the rate of the polymerization reaction (and (0Pr)d with different complexation ratios. (a) High Zrlp-
thus the viscosity increase) and the macroscopic proper- diketonate ratio; (b)low Zr/p-diketonate ratio. Reproduced by
ties of the coating^,^^,^^ these parameters have to be permission of Elsevier Publishing, from ref 45.
carefully balanced.
With the notion in mind that the hardness and the structure and texture of the derived organic-
abrasion resistance of such hybrid materials originates inorganic hybrid material^.^^
from the inorganic building blocks, the dimension of the Copolymerization with Organic (Macro-)Monomers.
inorganic phase and thus the hardness of coatings was The dimension of the organic structures and the degree
further increased by incorporating inorganic nanopar- of organic cross-linking in inorganic-organic hybrid
ticles, such as boehmite, zirconia, titania, or alumina.g0 polymers can be increased by copolymerizing the reac-
In a non-silicate system the effect of "diluting" a n tive groups of the organofunctional alkoxide 1 with
organofunctional alkoxide with the unsubstituted par- organic monomers or small oligomers. When hybrid
ent alkoxide was studied for methacryloxyethyl aceto- polymers are prepared from organofunctional alkoxides
acetate modified Zr(0Pr)s with different complexation 1, the cross-linking of all available organic groups is
ratios (Le., different ratios of, presumably, complex 24 often difficult, probably for sterical reasons. For ex-
(Figure 7 ) and unreacted Zr(OPr)4). Hybrid polymers ample, quantitative analysis of the photochemical poly-
were obtained after simultaneous sol-gel processing merization reaction in a n aged gel, obtained from a 1:l
and radical polymerization of the unsaturated organic mixture of MEMO and Si(OEt14, revealed that about
groups. Spectroscopic data indicated that a high Zr:/3- 20% of the initial double bonds remained unreacted.
diketonate ratio led to large zirconate building blocks However, addition of 2 equiv of methyl methacrylate
connected by short polymer chains, while with a low Zr: (MIHA) led to the complete polymerization of the meth-
P-diketonate ratio small oxide clusters are connected by acrylate groups from both sources (MEMO and MMA)
long polymer chains (Figure 9). The ratio between upon W irradiation.61
substituted and unsubstituted alkoxides thus controls The development of the hybrid structure in the
MEMO/Si(OEt)fiMA systemg2 was investigated by
differential scanning calorimetry and mechanical spec-
(91) Schmidt, H.; Seiferling, B.; Philipp, G.; Deichmann, K. In
Ultrastructure Processing of Advanced Ceramics; Mackenzie, J. D.,
Ulrich, D. R., Eds.; Wiley: New York, 1988. (92) Schmidt, H.; Philipp, G. J . Non-Cryst. Solids 1984, 63, 283.
Reviews Chem. Mater., Vol. 7, No. 11, 1995 2023

~ ~a related study with a hybrid polymer

t r o ~ c o p y .In glass fibres. W curing is possible in less than 0.1 s,
obtained from MEMO and propyl methacrylate, relax- even on a technical scale. The different modulus of
ation of the polymer in the range 100-400 K was elasticity and scratch resistance required for primary
attributed to the large-scale motion of the polyacrylate or secondary coatings was adjusted by the ratio of the
chains, the rotation of the ester groups, and configura- two si1anes.I
tional modification of the propyl groups.94 A scratch-resistant coating material for polycarbonate
The general idea behind the copolymerization of (for instance, compact disks) was developed by combina-
MEMO with acrylate monomers can, of course, also be tion of (Prn0)3Zr(methacrylate) or (PrnO)2Zr(meth-
applied to other reactive organic groups. For example, acrylate)^ with MEMO. MEMO was prehydrolyzed with
abrasion-resistant transparent coatings were prepared 1.5 mol equiv of water. Before use, 0.1-0.2 mol equiv
by crosslinking the epoxy groups of GLYMO with of one of the methacrylate-substituted zirconium alkox-
cycloaliphatic diepoxide monomers. The diepoxide and ides were added, and then the coatings were thermally
a cationic initiator were added to a sol obtained by acid- or photochemically cured.60,66Transparent monolithsg7
catalyzed sol-gel processing of a GLYMO/Si(OEt)4 and materials for optical and microoptical applications62
mixture. After coating on glass or polyethylene tere- were also prepared from the (Prn0)3Zr(methacrylate)/
phthalate, the films were dried and then UV cured. MEMO combination.
Mechanical properties of the films were found to be Materials Tailoring by Multicomponent Systems. In
dependent on type and amount of diepoxide. Films the previous paragraphs the different options for the
prepared without the diepoxide were brittle, while those preparation of sol-gel-derived organic-inorganic hybrid
with the diepoxide were flexible.95 There were two polymers were demonstrated. We now want to discuss
noteworthy findings about the epoxide polymerization: a few selected materials where a combination of these
A tighter silicate network retarded the polymerization, options was used to tailor materials properties. Al-
probably by restricting the diepoxide mobility. Second, though sometimes difficult to control, multicomponent
after triggering the cationic polymerization process by systems allow to some extent the fine-tuning of macro-
W light, it continued in the absence of light until it scopic materials properties, due to the specific functions
was limited by severe diffusion limitation^.^^ and properties of each component.
Recently, electrically conducting black hybrid poly- One of the earliest developments of organic-inorganic
mers were prepared from N-(3-(trimethoxysilyl)propyl)- hybrid polymers may illustrate this point. Major re-
pyrrole which, after sol-gel processing (with or without quirement for contact lenses are a good wettability and
Si(OEt)4),was oxidatively copolymerized with pyrrole.96 0 2 permeability, and sufficient scratch resistance, flex-
Hybrid Polymers from T w o Different Organofunc- ibility, and optical properties. Silicone materials do not
tional Alkoxide Precursors. The use of two different meet these requirements because they are hydrophobic.
organofunctional alkoxides can serve different pur- Therefore, GLYMO was prehydrolyzed, and then hy-
poses: (i) new ways for the cross-linking of the inorganic drophilic diol units were generated by controlled hy-
building blocks, (ii) modulation of the organic substruc- drolytic epoxide ring opening. Ti(ORI4 was added to
ture, or (iii) linking chemically different inorganic improve the mechanical properties of the obtained
building blocks, as illustrated by the following examples. materials and t o decrease shrinkage. At this stage of
A coating system for the mechanical protection of the development the materials had sufficient hydrophi-
plastics, particularly poly(methy1 methacrylate), was licity and 0 2 permeability, but were to brittle to be
obtained from (MeO)&-CH=CH2 (VTMS)and (Meoh- machined. Therefore, MEMO and methyl methacrylate
Si(CH&SH (MPTMS). Two cross-linking modes of the were added to generate a flexible polymethacrylate
organic groups are possible upon W irradiation: vinyl substructure by thermal polymerization. The resulting
groups may react with themselves to yield polymethyl- materials then exhibited all the required proper tie^.^^,^^
ene links between silicon atoms, or the -SH function A commercially available scratch- and abrasion-
may be added to a vinyl group to give -(CH&-S- resistant, corrosion-preventing coating system for brass
(CH2)3- links. When a 9 : l molar ratio of VTMS and is another example for this deliberate tailoring of
MPTMS was employed, vinyl polymerization prevailed. materials properties by combination of precursors with
Starting with equal amounts of the two silanes, the thiol different functions. The three components from which
addition reaction was dominating during the photo- it is composed have different functions: GLYMO allows
chemical curing. In the latter case, the coatings were the formation of flexible poly(ethy1ene oxide) chains
then cured in about half the time because this reaction during thermal curing. Al(OBu93 is the source for
is faster than vinyl polymerization. Owing to the alumina building blocks providing hardness, and a n
different chain lengths of the alternative links, the alkyltrimethoxysilane modifies the inorganic network
flexibility of the coating can be varied by the ratio of and reduces brittleness of the coating. Addition of a
the starting compounds.66 defined amount of water to a n alcoholic solution of the
Combination of the silanes 3a and 4 (Figure 1) three components gave a transparent lacquer, which
allowed the development of fast-curing primary and was then electrostatically sprayed to the brass items
secondary coatings with very good adhesion to optical and cured a t 130 "C. Adhesion to the metal surface was
very good, even after weathering, due to the covalent
(93) Cornu, J. F.; Etienne, S.; Mai, C.; Perez, J. J . Phys. N 1992, bonding between the metal surface and the coating.g9
C2-131.
(94) Mai, C.; Cornu, J. F.; Amaud, L.; Perez, J. J . Sol-Gel Sci.
Technol. 1994, 2, 135. (97) Nass, R.; Schmidt, H.; Arpac, E. SPIE, Sol-Gel Opt. 1990,1328,
(95) Sigel, G. A,; Domszy, R. C.; Welch, W. C. Mater. Res. Soc. Symp. 258.
Proc. 1994, 346, 135. (98) Schmidt, H.; Philipp, G. In Glass: Current Issues; Wright, A.
(96) Sanchez, C.; Alonso, B.; Chapusot, F.; Ribot, F.; Audebert, P. F., Dupuy, J., Eds.; Martinus Nijhoff Dordrecht, 1985; p 580.
J . Sol-Gel Sei. Technol. 1994, 2, 161. +
(99) Greiwe, K. farbe lack 1991, 11, 968.
2024 Chem. Mater., Vol. 7, No. 11, 1995 Reviews

A hybrid polymer with potential application for ul- drophilicity), respe~tive1y.l~~ These hybrid polymers are
trafiltration and reverse osmosis membranes was de- also very suitable hosts for a variety of organic dyes.
veloped from a mixture of four silanes with different They can be used for the low-temperature coloring of
functions. The first silane was prepared by reaction of glass, both for decorative, optical, and optoelectronical
(3-aminopropy1)triethoxysilanewith phthalic anhydride app1icati0ns.l~~
or pyromellitic dianhydride and provided the hydrophilic 2. Solid Electrolytes. Polymeric ion conductors are
function in the polymer. MEMO was added for the prepared by dissolving Li salts or strong acids in a
organic crosslinking of the hybrid polymer, and Ti(OP& polymer host matrix. Conductivity of these materials
to provide a higher mechanical resistance and a higher is often limited by partial crystallization of the polymers.
thermal stability. Finally, (MeOIsSiMe was used t o This problem was overcome by incorporating the Li+-
obtain silicone-like surface properties of the obtained solvating polymer in sol-gel-derived amorphous hybrid
material. loo polymer networks. MEMO and GLYMO were hydro-
Very versatile hybrid materials for applications in lyzed, and then ethyleneglycol diglycidyl ether was
microsystem technologies were prepared from a mixture added. Methylimidazole was used both as a catalyst for
of MEMO, GLYMO, Si(OEt)4, and VTMS or diphenyl- the sol-gel step and the copolymerization of the epoxide
silane diol.lol They show good to very good adhesion groups of GLYMO and the diglycidyl ether. Due to the
to a variety of substrates, such as steel, copper, alumi- presence of polyethylene oxide units, LiC104 is easily
num, silicon, glass, alumina, polyimide, or polyesters. dissolved in the hybrid polymer, which was cured as
Water vapour permeation rates are low and the electri- described above. The obtained material is amorphous
cal data very good. These materials were used, inter and can be applied as coatings or in bulk. The ion
alia, for passivation and encapsulation of electrical conductivity was 10-5 R-l cm-l a t 25 "C and R-l
components, as protective coatings for thin-film capaci- cm-l a t 125 'C.lo4 A modification of the above-
tors,lo2or as patternable coatings. Patterning is pos- mentioned material obtained from sulfonated MEMO
sible by different techniques, such as laser writing, or allyl(trimethoxy)silane also showed Lif conductiv-
proximity printing, contact printing, embossing, laser ity.lo5
ablation, or replication technology. The photolitho- As a n alternative to organic polymers, aminoalkyl-
graphic structuring procedure exemplarily illustrates substituted siloxanes made by sol-gel processing of
the functions of the different precursors. During sol- (Me0)3Si(CH2InNR2(for example, n = 3; NR2 = NH2,
gel processing the inorganic network is formed. The NH(CH&NH2, NH(CH2)2NH(CH2)2NH2)were investi-
thus-obtained coating lacquer was applied to the sub- gated. The obtained transparent, amorphous films are
strates by standard techniques. By structuring W stable in air up to 220 "C. Doping with CF3S03H
irradiation (masks or laser writing) the methacrylate resulted in proton conductivities up to 3 x 10-5 Q-l
groups of MEMO were polymerized. The nonexposed cm-l a t 25 "C and R-l cm-' a t 120 'C.lo6
parts of the coating was then dissolved by a developer Only cation conductivity is desired for many applica-
solution. Finally, the structured coating was thermally tions. An improved type of protonic electrolyte was
cured by polymerization of the epoxy groups of GLYMO. derived by grafting sulfonate anions to the phenyl
Very high aspect ratios were obtained by laser writing groups of poly(benzy1)siloxane. This was done by treat-
or mask aligning in the proximity mode.lol ing the material with chlorosulfonic acid after sol-gel
The idea of incorporating complementary functions processing of benzyl(trimeth0xy)silane. The plasticity
to the hybrid polymers by a n additional, organofunc- of this material had to be improved for applications as
tional precursor is demonstrated by the following ex- membranes in low-temperature fuel cells. This was
amples. The properties of the above mentioned scratch- achieved by co-condensation of (EtO)3SiCH*Ph,
resistant coating material for polycarbonate, obtained (Et013SiC~H13,and (Et013SiH. After sol-gel process-
by the combination of MEMO and methacrylate-modi- ing, the polymer was sulfonated as above and organi-
fied Zr(OPr14,were supplemented by fluorinated alkoxy- cally cross-linked by hydrosilylation of the Si-H groups
silanes of the type (R'0)3Si(CH2),(CF2)mCF3. Addition with divinylbenzene. Flexible membranes of about 100
of this alkoxide resulted in low-energy coatings with pm thickness were obtained with a n ac conductivity of
antisoiling proper tie^.^^ Functional coatings on glass 1.6 x lo-* W1 a t 25 'C.lo7 In a related approach, the
were varied by the same approach. Such coatings with polymeric hybrid polymer was prepared by sol-gel
good long-term adhesion to glass, scratch and abrasion processing of MEMO (or allyl(trimethoxy)silane), GLY-
resistance, and stability against weathering and cor- MO, and Si(OEt14. The sulfonyl groups were introduced
rosive delamination were prepared from MEMO, by adding variable amounts of sulfonated MEMO or
(EtO)sSiPh, and A U O B U ~for) ~ photochemical curing. allyl(trimethoxy)silane. Curing of the polymers was
Thermally curable coatings were obtained when GLY- done a s described before.lo5
MO was used instead of MEMO. The polarity of the 3. Materials Containing Covalently Bonded
surface was varied by addition of tridecafluorooctyltri- Organic Dyes. The possibility t o tailor the chemical
methoxysilane (increased hydrophobicity) or N-((2-ami-
noethyl)(3-aminopropyl))trimethoxysilane(increased hy- (103)Kron, J.; Amberg-Schwab, S.; Schottner, G. J . Sol-Gel Sei.
Technol. 1994, 2, 189.
(104) Popall, M.; Durand, H. Electrochim. Acta 1992, 37, 1593.
(100) Beslard, M. P.; Hovnanian, N.; Larbot, A,; Cot, L.; Sanz, J.; (105) Popall, M.; Du, X. Electrochim. Acta, in press.
Sobrados, I.; Gregorkiewitz, M. J . Am. Chem. Soc. 1991, 113, 1982. (106) Charbouillot, Y.; Ravaine, D.; Armand, M.; Poinsignon, C. J .
(101) Popall, M.; Kappel, J.; Pilz, M.; Schulz, J. Mater. Res. Soc. Non-Cryst. Solids 1988, 103, 325. Schmidt, H.; Popall, M.; Rousseau,
Symp. Proc. 1992,264, 353. Popall, M.; Kappel, J.;Schulz, J. In Micro F.; Poinsignon, C.; Armand, M.; Sanchez, J. Y. Proc. 2nd Int. Symp.
System Technologies '94; Reichl, H., Heuberger, A,, Eds.: vde-verlag: on Polymer Electrolytes; Scrosati, B , Ed.; Elsevier: London, 1990; p
Berlin, 1995. "-".
996
(102) Popall, M.; Kappel, J.; Pilz, M.; Schulz, J.; Feyder, G. J . Sol- (107) Gautier-Luneau, I.; Denoyelle, A,; Sanchez, J. Y.; Poinsignon,
Gel Sci. Technol. 1994, 2, 157. C. Electrochim. Acta 1992, 37, 1615.
Reviews Chem. Mater., Vol. 7, No. 11, 1995 2025
and physical properties of sol-gel materials, their (ii) Leaching of the dye is prevented by covalent
excellent optical quality, their low preparation temper- bonding to the sol-gel matrix. For example, a (Me0)aSi-
atures, and their easy deposition as coatings makes substituted rhodamine 110 derivative was prepared by
them ideally suited for optical applications. Extensive coupling the dye molecule with GLYMO. When
work on dyes embedded in sol-gel materials has been rhodamine 110 was embedded only in a sol-gel-derived
performed in the past 10 years and was reviewed silica matrix, leaching was a severe problem. When the
elsewhere.lo8 In a few cases, inorganic-organic hybrid dye was covalently bonded to the matrix, no leaching
sol-gel polymers were used a s a host for dyes. The was observed. Furthermore, a higher concentration of
above-mentioned hybrid polymer obtained from the the dye was achieved.l13
GLYMO and A1(OBus)3was recently shown to be a very (iii) The incorporation of NLO dyes in various organic
interesting host for laser dyes. By doping with YbCl3 polymer guest systems showed that chemical bonding
and dihydroxyanthraquinone (DAQ) or oxazine 170 (9- to the polymer provides for better stability of the
(ethylamino)-5-(ethylimino)-10-methyl-5H-benzo(a)- nonlinearity after alignment than physical doping.114
phenoxazonium perchlorate) materials for optical data Glasslike sol-gel matrixes appear to be even more
storage in the frequence domain were obtained. This suitable guests than organic polymers. Therefore, most
method allows the frequency-selective addressing of dye work on covalently bonded dye molecules in sol-gel
molecules embedded in a n amorphous matrix. To get matrixes was done with NLO chromophores.
high data-storage densities, line broadening caused by
a n interaction between the laser dye and the host has Noncentrosymmetric alignment of the chromophores
to be minimized. Doping of the sol-gel hybrid polymer inside sol-gel matrixes to achieve second-order nonlin-
was easily achieved by adding the dopants to the sol. earities was possible by corona poling, despite the more
The dyes are trapped in the hybrid network just by ionic character of sol-gel matrixes compared with
drying the material. Surprisingly narrow spectral holes classical polymers. Transparent films with large coef-
in the absorption bands of the dyes were generated by ficients for second harmonic generation (SHG) were
photophysical or photochemical hole-burning a t 2-50 obtained.
K. For the dihydroxyanthraquinoneKbCl3 complex the The effect of binding the dye to the oxide network was
hole width was about one-fifth of that found in a studied by preparing poled and cured films either by
ethanollmethanol glass matrix and almost 1 order of chemical binding of 6b (Figure 2) to a phenylsiloxane
magnitude smaller than that obtained with DAQ or its polymer or by incorporating the NLO dye disperse red
derivatives in organic polymers or amorphous inorganic 1 in the same matrix without chemical bonding. The
matrices.log former system had a much better stability. This was,
According to the scope of the present article, we will inter alia, attributed to restriction of the molecular
now discuss only those materials having the dye mol- motion of the segments, due to the bonding between the
ecules chemically bonded to the oxide matrix. This chromophore and the p01ysiloxane.l~A similar observa-
comparatively recent approach is still in development. tion was made when the stability of a sol-gel-derived
The chemical bonding of dye molecules to the oxide Ti02 film doped with 4-(2-(4-hydroxyphenyl)ethenyl)-
matrix requires its modification by E(OR'I3 (mostly N-methylpyridinium iodide and a film prepared by sol-
Si(OR'l3) containing groups (see Figure 2). This is gel processing of the corresponding (MeO)3Si-substituted
mostly not a trivial task, since the chromophor has to derivative 7b and Ti(OPr94 was ~ 0 m p a r e d . lThe
~ effect
remain undisturbed. Embedding organic dye molecules of covalently bonding the dye molecule to the matrix
in sol-gel materials without a chemical link is definitely was also probed by the trans-cis- trans isomerization
easier. Therefore, the chemical linking of the dye of azo compounds, which results in the reorientation of
molecules is only worthwhile if it results in a substan- the dipole moment of the active component. High
tially better performance of the resulting materials. values of birefringence were only observed when the dye
There are several potential benefits: was covalently bonded to the silicate matrix (sol-gel
processing of 6 o r related compounds and Si(OEt14).A
(i) The dye concentration in the final material can be large part of birefringence remained after the optical
considerably increased. For example, coloration of glass pump had been switched off,11 Somewhat contradictory
by anthraquinone or naphthoquinone doped sols is not results were obtained when the fluorescent dye pyrene
possible, because of their low solubility. This was not or its covalently bound derivative 8 was included in
a problem when (EtO)3Si-substituted phenoxazinium glasses or films prepared by fast sol-gel reaction of RSi-
and phenazinium dyes were used.lg It was demon- (OMe)3 (R = alkyl, phenyl). The fluorescence charac-
strated for several types of (R'0)3Si-functionalized NLO teristics showed that the chromophores were not ag-
dyes that the chemical bonding to the oxide network gregated and well dispersed throughout the product
allowed high dye concentrations without any crystal-
lization occuring.ll,l2,15,110-112 matrix. However, covalent attachment of the chro-
mophore did not result in any change in rotational or
diffusional mobility. The emission anisotropies for
(108) Avnir, D.; Braun, S.; Lev, 0.;Levy, D.; Ottolenghi, M. In Sol- glassy films containing pyrene or 8 were virtually
Gel Optics: Processing and Applications; Klein, L. C., Ed.; Kluwer
Academic: Dordrecht, 1994. identical. l8
(109) Schottner, G.; Grond, W.; Kiimmerl, L.; Haarer, D. J. Sol-
Gel Sci. Technol. 1994, 2, 657.
(110) Toussaere, E.; Zyss, J.;Griesmar, P.; Sanchez, C. Non-Linear (112) Griesmar, P.; Sanchez, C.; Puccetti, G.; Ledoux, I.; Zyss, J .
Opt. 1991,1,349. Sanchez, C.; Griesmar, P.; Toussaere, E.; Puccetti, Mol. Eng. 1991, I , 205.
G.; Ledoux, I.; Zyss, J. Non-Linear Opt. 1992, 2, 245. Puccetti, G.; (113) Snijkers-Hendrickx, I. J. M.; Oomen, M. W. J. L.; Wittouck,
Toussaere, E.; Ledoux, I.; Zyss, J.; Griesmar, P.; Sanchez, C. Polym. N.; De Schryver, F. Proc. 1st Europ. Workshop on Hybrid Organic-
Prepr. 1991, 32, 61. Inorganic Materials; Sanchez, C . , Ribot, F., Eds.; Pans, 1993; p 237.
(111) Kim, J.; Plawsky, J. L.; LaPeruta, R.; Korenowski, G. M. (114) Jungbauer, D.; Reck, B.; Twieg, R.; Yoon, D. Y.; Wilson, C.
Chem. Mater. 1992, 4, 249. G.; Swalen, J. D. Appl. Phys. 1990, 56, 2610.
2026 Chem. Mater., Vol. 7, No. 11, 1995 Reviews

The relaxation behavior of NLO chromophores strongly heterogenized metal complexes was given.z1
depends on the rigidity of the matrix, which is influ- Such metal complexes have the same spectroscopic
enced by the processing conditions and their composi- properties as the corresponding complexes with unmodi-
tion.'15 The optical response of films made from 7a and fied ligands in solution. In the known examples, the
Si(OEt)s was found to be strongly dependent on the structures of the complexes are therefore only insignifi-
poling voltage, the poling temperature, the substrate cantly altered by the modification of the ligand and by
resistivity, and the extent of polymerization. The sol heterogenization. This means that the silicate matrix
derived from only 7a was mainly composed of dimeric surrounding the metal complexes does not interact
species and linear chains with no cross-links. This significantly with the metal centers. The important
resulted in poor thermal stability of the SHG signal. difference of catalysts obtained by sol-gel processing of
Films made from 7dSi(OEt)d mixtures had a better metal complexes of the type [(R0)3Si-X-A],MLm (Fig-
stability but were still not satisfactory because the ure 3) is that the catalytically active metal moieties are
degree of cross-linking was limited.'l6 homogeneously distributed throughout the whole mate-
One approach to solve this problem was the use of rial. This has very beneficial effects on the catalyst
the inorganic-organic hybrid polymers discussed in the stability. Since the structure (porosity, surface area,
previous section as the matrix materials. They can be etc.) of the support can be tailored to some extent, the
hardened by organic and inorganic cross-linking after catalytically active centers are still accessible to the
poling. The azo dye 4-nitro-4'-((trimethoxysily1)pro- reactants. Therefore, the catalytic activity of the sol-
poxylazobenzene was added to a prehydrolyzed sol of gel catalysts is not inhibited, provided that the matrix
MEMO and (R0)3Zr(methacrylate). Films from this sol structure is appropriate.
were poled and then thermally or photochemically In another group of materials, organofunctional alkox-
cured. However, preliminary experiments did not result ides were used to immobilize metal ions. Sol-gel
in a substantially better optical response or stability, processing of metal alkoxides in the presence of metal
compared with organic polymers.'17 The presence of ions mostly does not result in a stable incorporation of
only one Si(ORI3 unit per chromophore makes the the metal ions into the resulting oxide materials. They
formation of a highly cross-linked sol-gel network very are eluted by water or alcohols. However, the leaching
difficult. The high mobility of the NLO dye in the free was prevented when organofunctional alkoxides capable
volume of the host network causes relaxation of the of coordinating the metal ions were added. The ethylene
poling-induced order. Another approach to improve the diamine derivative (Et0)3Si(CH2)3NHCHzCHzNHzproved
stability of the second-order optical nonlinearity there- to be very effective for anchoring Cd2', Co2', Cu2+,Ni2+,
fore was the use of multiple-substituted dyes such as Pd2+, or Pt2', while Ag+ was better coordinated by
6c (Figure 2). Although the stability of a poled and (Et0)3Si(CHzl3NHz or (Et0)3Si(CH2)3CN.25When one
cured film made from 6c and Si(OEt)4 was enhanced, of the organofunctional silanes and a metal salt are
further improvement was considered necessary. l4 In a mixed, metal complexes of the type [(R'0)3Si-
sol-gel film made from Si(OEtI4 and 4-methoxy-4'-(N- (CH2)&],Mn+ are formed in situ. Coordination of the
~3-triethoxysilylpropyl~carboxymethyl)azobenzene, at- metal ions is retained during sol-gel processingz5 and
tachment of the chromophore to the silicate matrix had even in aerogels after supercritical drying.52 The sub-
slight effect on photochemical trans-cis as well as stituted thiourea (Et0)3Si(CH2)3NHC(S)NHPhwas pre-
thermal cis-trans isomerizations, whereas the photo- pared by reaction of (Et0)3Si(CH2)3NHz with PhNCS
isomerization was markedly suppressed when the and was used to coordinate Pd2' ions.lZ0
azobenzene was fixed to the matrix a t both ends of the Modification of non-silicon alkoxides with diamino
chromophore.13 It was later found that the isomeriza- carboxylates resulted in the organofunctional alkoxides
tion kinetics of these azo dyes is different in sol-gel (RO),E(OOC(HZN)C-X-NH~)(Figure 31, which can be
films and bulk materials. The larger free volume in the analogously used to immobilize metal ions by formation
bulk material was attributed to larger pores.'l8 of complexes of the type [(RO),E-X-A],Mn-.43
New photochromic hybrid materials were recently In a related approach, organofunctional alkoxysilanes
prepared by sol-gel processing of Si(OEt)4, silanol- were used to stabilize small CdS or metal clusters in
terminated dimethylsiloxane oligomers and (triethoxy- sol-gel matrixes.lZ1
sily1)propyl-substitutedspirobenzopyranes. The trans- 5. Sensors. The alternative methods used for the
parent gels exhibited the normal p h o t o c h r ~ m i s m . ~ ~ ~ immobilization of dyes or catalysts can also be used for
4. Metal-Containing Materials. The sol-gel the preparation of sol-gel-derived sensors: doping,
method is a n attractive possibility for the heterogeni- covalent bonding to the preprepared matrix, or co-
zation of homogeneous metal complex catalysts by condensation of modified precursors. The advantages
anchoring them on silica as a solid support. A much and disadvantages of these methods for sensor applica-
higher metal loading can be achieved than with other tions were discussed in a recent article.lzZ Following
methods. Work in this area was recently reviewed in the general intention of the present article, we will again
another article, where also a list of selected sol-gel only discuss the preparation of those sensor materials
in which (RO),E-substituted precursors are involved.
(115) Leheau, B.; Maquet, J.;Sanchez, C.; Toussaere, E.; Hierle,
R.; Zyss, J. J . Mater. Chem. 1994,4,1855. (120) Ferrari, C.; Predieri, G.; Tiripicchio, A. Chem. Mater. 1992,
(116) Kim, J.; Plawsky, J. L.; Van Wagenen, E.; Korenowski, G. 4,243.
M. Chem. Muter. 1993,5,1118. (121)Spanhel, L.; Arpac, E.; Schmidt, H. J . Non-Cryst. Solids 1992,
(117) Kador, L.; Fischer, R.; Haarer, D.; Kasemann, R.; Briick, S.; 147,148, 657. Schmidt, H. K. Muter. Res. SOC.S y m p . Proc. 1992,274,
Schmidt, H.; Diirr, H. Adu. Muter. 1993,5,270. 121. Choi, K. M.; Shea, K. J. Muter. Res. SOC.Symp. Proc. 1994,346,
(118)Ueda, M.; Kim, H.-B.; Ichimura, K. Chem. Muter. 1994,6 , 763. Burkhart, T.; Mennig, M.; Schmidt, H.; Licciulli, A. Mater. Res.
1771. SOC.S y m p . Proc. 1994,346,779.
(119)Nakao, R.; Ueda, N.; Ahe, Y.; Horii, T.; Inoue, H. Polym. Adu. (122) Lev, 0.;Tsionsky, M.; Rahinovich, L.; Glezer, V.; Sampath,
Technol. 1994,5, 240. S.; Pankratov, I.; Gun, J. Anal. Chem. 1995,67,22A.
Reviews Chem. Mater., Vol. 7, No. 11, 1995 2027

The sensitive layers of SO2 gas sensor systems were by sol-gel processing, the development of membranes
synthesized from a 7:3 mixture of (Et0)3Si(CH2)3NR2 from hybrid polymers is in its infancy. Apart from a
( R = Me, Et) and (Et0)3SiPrn. The adsorption mech- poorly documented early attempt,129only few, very
anism is presumably the formation of a weak adduct recent reports are available. This is, nevertheless, a
between the amino group of the silane and S02. The very promising area of development, because the pos-
propylsilane reduced the hydrophilic character of the sibility of forming mechanically stable membranes by
materia1.65J23J24A sensor system with a n integrated inorganic polycondensation is implemented by the pos-
optical device was described, based on changes of the sibility t o incorporate organic functions.
refractive index of the sensitive layer upon gas adsorp- Hybrid polymers prepared by coupling (Et0)aMeSi-
tion. The sensor can only be used under special condi- (CH213NHz or (Et0)3Si(CH2)3NH2 with terephthaloyl
tions, because some other gases, especially NO2 or NH3, chloride and sol-gel processing of the thus-obtained
cause irreversible r e a ~ t i 0 n s . lAnother
~~ system consists precursors [ ( E ~ O ) ~ R S ~ ( C H ~ ) ~ N H C(precursor
(~)I~CSH~
of two different transducers for the same material. The A: R = Me, precursor B: R = OEt) were casted on
ambiguity of a single sensor signal a t higher SO2 alumina supports.28 A dense structure was obtained for
concentrations was avoided by integrating both a di- the material prepared from precursor A, in which gas
electric sensor and a mass sensor in the system.123 Two molecules can solubilize and diffuse under a pressure
gas-sensitive layers for different SO2 concentration gradient. Therefore, membranes prepared from this
ranges were developed in another work: for low con- materials have gas separation ability. Due to their more
centration ( ~ ppm)
2 based on (Et0)3Si(CH2)3NMe2,and hydrophilic character, membranes prepared from pre-
for concentrations up to 6000 ppm based on (Et0)sSi- cursor B were better suited for nanofiltration. Facili-
( C H ~ ) S N EA~slight
~ . ~ modification,
~~ replacement of the tated transport membranes were obtained by co-
N R 2 group in the starting silane by NH2, resulted in a condensation of precursor A with the substituted crown
material suitable for the detection of C02.124 ether 15 (Figure 4).28 The transport selectivity of K+
A (MeO)3Si-substituted derivative of methyl red [(p- over Li' was about 4 and only due to the presence of
M~~N)C~H~-N=N-(C~H~-O-CO O Hprepared
was )] by the crown ether moieties. Since the selectivity is in good
coupling of the COOH groups with (Me0)3Si(CH2)3NH2. agreement with the properties of benzo-15-crown-5, the
The alkoxysilyl derivative was used to prepare a sensor character of the carrier was not changed by incorpora-
with a nonleachable pH indicator.126 tion into the membrane. Transport is facilitated by
In another approach to prepare a sol-gel-derived pH lipophilic counteranions, indicating that ion pairs are
sensor, fluorescein was added to sols made from either carried.28
Si(OEt14 or a n organically modified alkoxysilane (pre-
pared by coupling (Et0)3Si(CH2)3NH2with terephthal- A covalently bonded monolayer of the silane am-
oyl chloride). While the purely inorganic material gave phiphile 16 (Figure 4) was immobilized on a porous glass
promising results in terms of stability, repeatability, and plate by the Langmuir-Blodgett technique. The lipid
monolayer acted as a gate membrane for permeation of
response time, the hybrid polymer proved to be less
ions and water-soluble fluorescent probes. The corre-
suited.127
Within the framework of the development of a n sponding single- or triple-chain silane amphiphiles (one
optical immunosensor, a sol prepared from (Et0)sSi- or three CH3(CH2)17 units instead of two) were not
(CH2)sA (A = NHMe, NH2, or SH) was coated on gold- suitable for this purpose.29
coated glass surfaces. After activation of the organo-
functional hybrid polymer films in aqueous buffers by Conclusions
bifunctional coupling agent, immunoglobulin was co-
valently anchored to the transducer surface with a n Materials with a variety of potential applications can
optimal stability and biological activity.128 be prepared starting from organofunctional metal alkox-
6. Membranes. While considerable progress has ide precursors. Most applications are in a rather early
been made in the preparation of ceramic membranes stage, except the development of inorganic-organic
hybrid polymers. The many possibilities of chemically
(123) Endres, H.-E.; Mickle, L. D.; Kosslinger, C.; Drost, S.; Hutter,
modifying the precursor systems and the inherent
F. Sensors Actuators B 1992,6, 285. advantages of the sol-gel process allow the deliberate
(124) Brandenburg, A.; Edelhauser, R. Sensors Actuators B 1993, tailoring of materials properties in a wide range. Most
11, 361.
(125) Lin, J.; Moller, S.; Obermeier, E. Sensors Actuators B 1991, materials developments are presently based on alkoxy-
5,219. silanes. To fully exploit the wealth of this approach for
(126) Aharonson, N.; Altstein, M.; Avidan, G.; Avnir, D.; Bronshtein, materials syntheses, the underlying chemistry, particu-
A,; Lewis, A,; Liberman, K.; Ottolenghi, M.; Polevaya, Y.; Rottman,
C.; Samuel, J.;Shalom, S.; Strinkovski, A,; Turniansky, A. Mater. Res. larly of non-silicon alkoxides, has to be further developed.
SOC.Symp. Proc. 1994,346, 519.
(127) Lacan, P.; Le Gall, P.; Rigola, J.; Lurin, C.; Wettling, D.; CM9502636
Guizard. C.: Cot. L. SPIE. Sol-Gel Oat. 1992.1758. 464.
(128)'Collino,'R.; Therasse, J.;Biider, P.; Chaput, F.; Boilot, J.-P.;
Levy, Y . J . Sol-Gel Sci. Technol. 1994,2, 823. (129) Kaiser, A,; Schmidt, H. J . Membr. Sci. 1985,22, 257.