Journal of Porphyrins and Phthalocyanines Published at http://www.worldscinet.

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J. Porphyrins Phthalocyanines 2009; 13: 235–246

Synthesis and properties of macrodiscotic triphenyleno-

phthalocyanines

Andrew N. Cammidge*š and Hemant Gopee

School of Chemical Sciences and Pharmacy, University of East Anglia, Norwich NR4 7TJ, United Kingdom

Received 16 September 2008

J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

Accepted 10 October 2008

ABSTRACT: Phthalocyanines present a flat, disk-like molecular profile and suitably substituted derivatives
show discotic liquid crystalline behavior. Extension of the molecular π-system through benzofusion perturbes
the phthalocyanine’s basic properties, most notably shifting the absorption to longer wavelength. This paper
describes our synthesis of triphenylenophthalocyanines where the benzene rings of phthalocyanines are
replaced by triphenylene units. The resulting materials are macrodiscotic in nature. They show red-shifted
absorption spectra and columnar mesophase behavior over a wide temperature range.
KEYWORDS: phthalocyanines, triphenylenes, macrodiscotic, columnar mesophase.

INTRODUCTION structures have emerged alongside phthalocyanine and

perhaps the most widely studied materials are based on
Phthalocyanine [1] synthesis remains an area of triphenylene cores [6]. Interest in triphenylene based dis-
intense research effort. New and often elaborate deriva- cotic liquid crystals stems in part from their ability to act
tives are constantly being reported. For the most part, as efficient, one-dimensional conductors in addition to
the synthesis of new phthalocyanines is driven by desire their diverse mesophase behavior [7]. Extended phtha-
to tune, control or investigate their materials properties, locyanines are known to give rise to perturbed proper-
frequently with a specific application in mind. For even- ties. In particular, extension of the molecule’s π-system
tual application it is usually important for a final mate- results in longer wavelength electronic absorption (red-
rial (phthalocyanine) to be easily processable, requiring shifted spectra) and a number of fused and modified
solubility in common solvents. Solubility can often be core structures are now known where, for example, the
achieved by introducing functional groups (typically benzene units of parent phthalocyanines are replaced by
alkyl or alkoxy substituents) around the phthalocyanine naphthalene, anthracene or perylene [8]. We reasoned
[2]. More than 25 years ago it was discovered that cer- that combination of the triphenylene and phthalocyanine
tain substituted phthalocyanines displayed liquid crys- cores could give rise to interesting materials (Fig. 1) [9].
talline properties [3] and were part of the then recently
discovered class of discotic liquid crystals [4]. Exhibi-
tion of discotic (and particularly columnar) mesophase RESULTS AND DISCUSSION
behavior extends the usefulness of phthalocyanines as
molecular materials. Liquid crystals are self-assembling
Synthesis
and self-healing structures and provide a mechanism for
overcoming defect issues which frequently hinder device The vast majority of phthalocyanine syntheses employ
development from promising molecular materials. the corresponding dinitrile (phthalonitrile) as precur-
The field of discotic liquid crystals has itself grown sor. Although the final step (synthesis of the phthalo-
in parallel to phthalocyanine synthesis [5]. Many core cyanine) is itself frequently difficult, most synthetic
challenge and effort revolves around preparation of the
š
SPP full member in good standing dinitrile precursor. In designing the synthesis of target
*Correspondence to: Andrew N. Cammidge, email: a.cammidge@ triphenylenophthalocyanine structures 1–3 we were able
uea.ac.uk, fax: +44 (0)1603592011 to take advantage of developments from our laboratory

Copyright © 2009 World Scientific Publishing Company

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 236 A. N. CAMMIDGE AND H. GOPEE

RO OR RO OR

RO OR RO OR

OR OR OR OR
RO N OR RO N OR
N N N N N N N
N Zn N N Zn N N Zn N
N N N N
N N N RO
N
OR
N
RO OR
OR OR OR OR

RO OR RO OR
RO OR RO OR
1 2 3
Fig. 1. Macrodiscotic triphenylenophthalocyanines

whereby selective syntheses of differentially substituted triphenylenophthalocyanines could not be isolated pure.
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

triphenylenes had been developed [10]. Construction of The zinc phthalocyanines themselves proved challenging
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

triphenylene dinitriles employed palladium-catalysed to purify but pure samples were obtained by careful col-
cross-coupling procedures in key steps. The two classes of umn chromatography. Yields for the dodecyloxy deriva-
octaalkoxytriphenylenophthalocyanines 1 and 2 were syn- tives were considerably lower than for the shorter chain
thesized following closely related strategies (Scheme 1). analogues.
Bromophenols 4 and 22 were alkylated and converted
to their corresponding boronic acids via the Grignard
Characterization
reagents. The boronic acids were coupled [11] with
dibromoveratrole 9 to yield terphenyls 10, 11, 27 and 28. Pure samples of the triphenylenophthalocyanines
Terphenyls 10 and 11 were easily converted to the cor- were obtained by careful column chromatography and
responding triphenylenes 12 and 13 by oxidative cycliza- reprecipitation, giving satisfactory elemental analy-
tion using iron chloride in dichloromethane [10, 12]. The sis and mass spectra. NMR spectra were more difficult
isomeric terphenyls 27 and 28 could not be cyclized in the to obtain however. The materials are soluble in com-
same way and a more tedious photochemical procedure mon organic solvents but the peaks in the NMR spectra
was required [13]. Methyl ethers were selectively hydro- are severely broadened, indicating strong tendency of the
lyzed using lithium diphenyl phosphide [14] and diols molecules to aggregate. Attempts were made to improve
14, 15, 31 and 32 were converted into their triflate esters the resolution of the spectra through addition of pyri-
with triflic anhydride. The conversion of aryl triflates to dine and elevated temperature. However, the spectral
nitriles using palladium catalysis has been developed as a change was minimal, which underlines the aggrega-
synthetic procedure over recent years [15]. Its application tion strength. This aggregation is even observed at the
to the conversion of triphenylene triflates into dinitriles low concentrations employed in UV-vis spectroscopy
18, 19, 35 and 36 was successful but the reactions proved also. The spectra of the phthalocyanines show red-shifts
extremely capricious. To some extent this is not surprising compared to normal phthalocyanines and are typical of
because electron-rich substrates (such as our alkoxytri- metallophthalocyanines. A shift of λmax of 50–90 nm is
phenylenes) do not favor cross-coupling reactions [11]. observed compared to unsubstituted zinc phthalocyanine
An alternative strategy (Scheme 2) was therefore inves- (Fig. 2).
tigated using dichlorophthalonitrile. Palladium-catalysed An investigation of the mesophase behavior of these
cross-coupling of boronic acids 7 and 8 with dichlo- macrodiscotic phthalocyanines, by polarizing optical
rophthalonitrile was also successful but again the reac- microscopy of thin films between glass slides, shows
tion proved capricious and low-yielding. The isomeric that they all form viscous liquid crystal phases. In the
para-substituted boronic acids failed to react at all. hexyloxy series, triphenylenophthalocyanine 37 has a
Hexadecaalkoxytriphenylenophthalocyanine structures high melting point (270 °C) whereas its isomer 20 melts
3 were prepared following an alternative pathway at 185 °C. Both are liquid crystalline beyond 300 °C.
(Scheme 3). Biphenyl 44 was coupled directly with vera- The most heavily substituted derivative 53 exhibits an
trole to give tetramethoxytriphenylene 46. Bromination extremely wide mesophase range and is liquid crystal-
followed by palladium catalyzed cross coupling with zinc line at room temperature to beyond 300 °C. The trend
cyanide [16] gave dintriles 51 and 52 directly. in the dodecyloxy series is for lower melting points with
Synthesis of all phthalocyanines was achieved by 38 melting at 100 °C and 21 melting at 60 °C. Once
refluxing the corresponding dinitrile in hexanol with again the triphenylenophthalocyanine with 16 substitu-
zinc acetate and DBU. Reactions performed without a ents is liquid crystalline at room temperature. All three
zinc template were very low-yielding and metal-free remain liquid crystalline to at least 300 °C (Fig. 2).

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 236–246

00026.indd 2 4/3/2009 6:38:51 AM

 SYNTHESIS AND PROPERTIES OF MACRODISCOTIC TRIPHENYLENOPHTHALOCYANINES 237

OR OR
Br OMe
OH OR OR
Br OMe OMe
9 FeCl3 OMe LiPPh2
Br Br B(OH)2 Pd OMe OMe

4 5 R = C6H13 7 R = C6H13 10 R = C H 12 R = C6H13

6 R = C12H25 8 R = C12H25 OR 11 R = C6 H13 OR 13 R = C H
12 25 12 25

RO OR
OR OR OR
ROH OR OR
DBU
OH Tf2O OTf ZnCN2 CN Zn(OAc)2 N N N

OTf Pd N Zn N
OH CN
N N N
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

OR OR OR OR OR
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

14 R = C6H13 16 R = C6H13 18 R = C6H13

15 R = C12H25 17 R = C12H25 19 R = C12H25 RO OR

20 R = C6H13
21 R = C12H25

Br OMe
1. Mg RO RO
OH OR 2. B(OMe)3 OR
Br OMe
RBr 3. H+ OMe hν, I2 OMe LiPPh2
Pd
OMe OMe
Br
Br B(OH)2 RO RO
22 23 R = C6H13 25 R = C6H13 27 R = C6H13 29 R = C6H13
24 R = C12H25 26 R = C12H25 28 R = C12H25 30 R = C12H25
RO OR

RO RO
RO ROH
OH Tf2O OTf ZnCN2 DBU RO OR
CN Zn(OAc)2 N N N
OH OTf Pd N Zn N
CN
RO RO N N N
RO RO OR
31 R = C6H13 33 R = C6H13 35 R = C6H13
32 R = C12H25 34 R = C12H25 36 R = C12H25
37 R = C6H13
38 R = C12H25
RO OR
Scheme 1. Synthesis of octaalkoxytriphenylenophthalocyanines

OR OR
Cl CN
OR
Cl CN CN FeCl3 CN
39
B(OH)2 CN CN
Pd

7 R = C6H13 OR 40 R = C6H13 OR 18 R = C6H13

8 R = C12H25 41 R = C12H25 19 R = C12H25
Scheme 2. Alternative synthesis of dinitrile precursors

The compounds do not form isotropic liquids at access- Annealed samples at elevated temperatures tend to align
able temperatures so it was not possible to characterize homeotropically, with bright birefringence observed
the mesophases further by texture analysis. However, it is when the sample is sheared. The formation of such sta-
clear that the mesophases are all columnar (not nematic). ble mesophases can be linked to the strong aggregation

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 237–246

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 238 A. N. CAMMIDGE AND H. GOPEE

OMe OR
OMe
MeO RO
Br MeO
1. HBr/HOAc
Pd 45 2. RBr/K2CO3 Br2

FeCl3
OMe
OMe B(OH)2 OMe
MeO RO 47 R = C6H13
42 43 OMe 44 OMe 46 OR
48 R = C12H25

RO OR

OR OR RO OR
RO RO ROH
Zn(CN)2 DBU
OR OR
Br Pd CN Zn(OAc)2
RO OR
N N N
Br CN
N Zn N
RO RO
OR OR N N N
RO OR
OR OR
49 R = C6H13 51 R = C6H13
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50 R = C12H25 52 R = C12H25
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

53 R = C6H13 RO OR
54 R = C12H25 RO OR
Scheme 3. Synthesis of hexadecaalkoxytriphenylenophthalocyanines

RO OR
RO OR
RO OR RO OR

OR OR OR OR
RO OR RO OR
N N N N N
N N N N
N Zn N N Zn N N Zn N
N
N N N N N N N N
RO OR RO OR
OR OR OR OR

RO OR RO OR
RO OR RO OR

λmax = 745 nm λmax = 748 nm λmax = 765 nm

Mesophase behaviour Mesophase behaviour Mesophase behaviour

o o
20 R = C6H13 LC> 185 C 37 R = C6H13 LC> 270 C 53 R = C6H13 LC> 20 oC
21 R = C12H25 LC> 60 oC 38 R = C12H25 LC> 100 oC 54 R = C12H25 LC> 20 oC

Fig. 2. Liquid crystal and absorption properties (THF) of triphenylenophthalocyanines

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 238–246

00026.indd 4 4/3/2009 6:38:52 AM

 SYNTHESIS AND PROPERTIES OF MACRODISCOTIC TRIPHENYLENOPHTHALOCYANINES 239

behavior observed in solution phase as it is to be expected Me4Si): δH, ppm 7.12 (2 H, dd, J = 8.0, 7.8 Hz), 6.95
that the macrodiscotic, extended planar π-systems would (2 H, s), 6.75–6.67 (6 H, m), 3.93 (3 H, s), 3.74 (4 H, t,
tend to form strong cofacial aggregates. J = 6.6 Hz), 1.70–1.61 (4 H, m), 1.56–1.24 (12 H, m),
0.87 (6 H, t, J = 6.7 Hz). 13C NMR (75.45 MHz, CDCl3,
Me4Si): δC, ppm 182.8, 148.4, 143.1, 133.2, 129.1, 122.4,
EXPERIMENTAL 116.2, 113.7, 113.3, 68.0, 56.2, 31.6, 29.2, 25.7, 22.7,
1-bromo-3-hexyloxybenzene 5. 3-bromophenol 4 14.1. MS (EI): m/z 490. Calcd. for [M]+ 490.
(50 g, 0.29 mol), 1-bromohexane (71.6 g, 0.43 mol) and 6,11-bis(hexyloxy)-2,3-dimethoxytriphenylene 12.
anhydrous potassium carbonate (60 g, 0.43 mol) were 3,3′′-bis(hexyloxy)-4′,5′-dimethoxy-[1,1′,2′,1′′]-terphenyl
heated in refluxing ethanol (250 mL) under nitrogen for 10 (3.86 g, 7.88 mmol) was dissolved in dichloromethane
24 h. The solution was filtered, dilute hydrochloric acid (100 mL) and iron (III) chloride (3.20 g, 0.020 mol)
was added to the filtrate, and the mixture extracted with added. The mixture was stirred at room temperature for
ethyl acetate (3 × 150 mL). The solvent was removed in 2 h and methanol and water added. The mixture was
vacuo and the residue distilled under reduced pressure extracted with dichloromethane (3 × 100 mL) and the
(126 °C, 1 mm Hg) to give the pure title compound. Yield solvents removed in vacuo. The residue was purified by
69.55 g (94%). 1H NMR (300 MHz, CDCl3, Me4Si): δH, column chromatography (eluting with dichloromethane/
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

ppm 7.12–7.04 (3 H, m), 6.84 (1 H, d, J = 1.3 Hz), 3.91 petroleum ether, 1:1) and recrystallization from ethanol to
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

(2 H, t, J = 6.6 Hz), 1.79–1.74 (2 H, m), 1.44–1.30 give the pure title compound as colorless crystals. Yield
(6 H, m), 0.92 (3 H, t, J = 6.7 Hz). 13C NMR (75.45 MHz, 2.20 g (57%); mp 134 °C. Anal. calcd. for C32H40O4: C,
CDCl3, Me4Si): δC, ppm 160.3, 130.7, 123.7, 122.9, 78.69; H, 8.20%. Found: C, 78.66; H, 8.20. 1H NMR
117.9, 113.7, 68.3, 31.6, 29.1, 25.7, 22.6, 14.0. (300 MHz, CDCl3, Me4Si): δH, ppm 8.46 (2 H, d, J =
3-hexyloxyphenylboronic acid 7. 1-bromo-3-hexyl- 9.1 Hz), 7.89 (2 H, s), 7.86 (2 H, d, J = 2.3 Hz), 7.20
oxybenzene 5 (50 g, 0.195 mol) was added dropwise to (2 H, dd, J = 9.1, 2.3 Hz), 4.20–4.12 (10 H, m), 1.92–1.87
a suspension of magnesium turnings (4.74 g, 0.195 mol) (4 H, m), 1.42–1.37 (12 H, m), 0.93 (6 H, t, J = 6.7 Hz).
in THF (150 mL) under nitrogen so as to maintain gentle 13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 157.9,
reflux of the THF. After addition, the reaction mixture 149.4, 129.8, 124.3, 124.2, 123.3, 114.5, 106.9, 104.7,
was further refluxed for 3 h. The Grignard reagent was 68.2, 55.9, 31.5, 29.3, 25.7, 22.4, 13.8. MS (EI): m/z 488.
cooled down to room temperature and transferred to a Calcd. for [M]+ 490.
solution of trimethylborate (40.5 g, 0.39 mol) in THF 6,11-bis(hexyloxy)triphenylene-2,3-diol 14. Diphe-
(150 mL) at -78 °C. The reaction mixture was then nylphosphine (1.0 mL, 5.78 mmol) was stirred in THF
allowed to warm up to room temperature overnight. (30 mL) under nitrogen at 0 °C. Cold butyllithium (2.5 M,
Dilute hydrochloric acid (300 mL, 1 M) was added and 3 mL, 6.4 mmol) was slowly added and the mixture allowed
the mixture extracted with diethylether (3 × 150 mL). The to warm to room temperature. 7,10-bis(hexyloxy)-2,3-
organic extracts were dried over MgSO4 and the solvent dimethoxytriphenylene 29 (1.0 g, 2.0 mmol) was added
removed under reduced pressure. The solid was recrystal- and the mixture stirred at room temperature for 24 h.
lized from petroleum ether to give pure title compound. Dilute sulfuric acid was carefully added and the mixture
Yield 22.35 g (52%); mp 58 °C. 1H NMR (300 MHz, extracted with ethyl acetate (4 × 150 mL). The solvent
CDCl3, Me4Si): δH, ppm 7.81 (1 H, dd, J = 7.1, 2.5 Hz), was evaporated and the crude product purified by column
7.73 (1 H, t, J = 2.5 Hz), 7.42 (1 H, dd, J = 9.0, 7.1 Hz), chromatography (eluting with ethyl acetate/petroleum
7.12 (1 H, dd, J = 9.0, 2.5 Hz), 4.06 (2 H, t, J = 6.5 Hz), ether, 1:4) to give the pure title compound as a white
1.89–1.75 (2 H, m), 1.59–1.33 (6 H, m), 0.90 (3 H, t, solid. Yield 0.66 g (70%); mp 154–158 °C. 1H NMR (300
J = 7.0 Hz). MHz, CDCl3, Me4Si): δH, ppm 8.41 (2 H, d, J = 9.2 Hz),
3,3′′-bis(hexyloxy)-4′,5′-dimethoxy-[1,1′,2′,1′′]- 7.96 (2 H, s), 7.77 (2 H, d, J = 2.5 Hz), 7.18 (2 H, dd,
terphenyl 10. 3-hexyloxyphenylboronic acid 7 (11.18 g, J = 9.2, 2.5 Hz), 5.56 (2 H, br), 4.12 (4 H, t, J = 6.6 Hz),
0.051 mol), 1,2-dibromo-4,5-dimethoxybenzene 9 (5.0 g, 1.88–1.81 (4 H, m), 1.55–1.35 (12 H, m), 0.93 (6 H, t, J =
0.017 mol), sodium carbonate (8.05 g, 0.08 mol), triphe- 7.0 Hz). 13C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm
nylphosphine (0.30 g, 1.01 mmol) and palladium chloride 157.8, 144.4, 129.9, 125.2, 124.5, 123.5, 115.8, 109.1,
(0.09 g, 0.50 mmol) were stirred in a refluxing mixture of 106.4, 68.5, 31.7, 29.5, 25.9, 22.7, 14.1.
toluene, ethanol and water (3:3:1 respectively, 200 mL) 6,11-bis(hexyloxy)triphenylene-2,3-ditriflate 16. 6,11-
under nitrogen for 24 h. Water was added and the mix- bis(hexyloxy)triphenylene-2,3-diol 14 (1.0 g, 2.0 mmol)
ture extracted with dichloromethane (3 × 150 mL). The was added to dry dichloromethane (50 mL) and pyridine
solvent was removed in vacuo to leave a dark-brown oil (0.70 mL, 8.0 mmol) at -20 °C. Trifluoromethanesul-
which was purified by column chromatography (elut- phonic acid anhydride (2.4 mL, 15 mmol) was slowly
ing with dichloromethane/petroleum ether, 1:4) to give added to the solution and the mixture allowed to warm to
the pure title compound as a colorless oil. Yield 6.38 g room temperature overnight. Dilute hydrochloric acid was
(78%). Anal. calcd. for C32H42O4: C, 78.36; H, 8.57%. added and the mixture extracted with dichloromethane
Found: C, 78.13; H, 8.54. 1H NMR (300 MHz, CDCl3, (3 × 150 mL). The solvent was removed in vacuo and the

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 239–246

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 240 A. N. CAMMIDGE AND H. GOPEE

residue purified by column chromatography (eluting with 190 °C. Anal. calcd. for C32H34N2O2: C, 80.30; H, 7.16;
dichloromethane/petroleum ether, 1:4) and recrystalliza- N, 5.85%. Found: C, 80.30; H, 7.10; N, 5.83. IR (Nujol):
tion from ethanol to give the pure title compound. Yield νmax, cm-1 2230 (CN). 1H NMR (300 MHz, CDCl3, Me4Si):
1.0 g (64%); mp 103 °C. Anal. calcd. for C32H34O8S2F6: δH, ppm 8.87 (2 H, s), 8.47 (2 H, d, J = 9.2 Hz), 7.83 (2 H,
C, 53.04; H, 4.78% Found: C, 53.10; H, 4.70. 1H NMR d, J = 2.5 Hz), 7.39 (2 H, dd, J = 9.2, 2.5 Hz), 4.19 (4 H,
(300 MHz, CDCl3, Me4Si): δH, ppm 8.54 (2 H, s), 8.47 t, J = 6.5 Hz), 1.92–1.89 (4 H, m), 1.59–1.36 (12 H, m),
(2 H, d, J = 9.2 Hz), 7.80 (2 H, d, J = 2.5 Hz), 7.35 (2 H, 0.94 (6 H, t, J = 6.7 Hz). 13C NMR (75.45 MHz, CDCl3,
dd, J = 9.2, 2.5 Hz), 4.18 (4 H, t, J = 6.4 Hz), 1.93–1.86 Me4Si): δC, ppm 158.7, 132.8, 130.1, 127.5, 125.4, 124.9,
(4 H, m), 1.56–1.38 (12 H, m), 0.94 (6 H, t, J = 7.0 Hz). 119.7, 116.4, 111.9, 106.7, 68.7, 60.0, 31.7, 29.8, 25.8,
13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 158.5, 22.6, 14.1. MS (EI): m/z 478. Calcd. for [M]+ 478.
138.3, 129.8, 124.9, 124.5, 121.8, 118.8, 118.0, 107.5, Octa(hexyloxy)triphenylenophthalocyanine 20. 6,11-
68.7, 60.0, 31.8, 29.4, 25.9, 22.7, 14.1. MS (EI): m/z 724. bis(hexyloxy)-triphenylene-2,3-dicarbonitrile 18 (0.80 g,
Calcd. for [M]+ 724. 1.67 mmol) was dissolved in 1-hexanol and DBU (0.18 g,
3,3′′-bis(hexyloxy)-[1,1′;2′,1′′]terphenyl-4′,5′- 1.17 mmol) added. The solution was refluxed for 1 h
dicarbonitrile 40. 4,5-dichlorophthalonitrile 39 (5.00 g, and zinc acetate (0.10 g, 0.42 mmol) added. The solu-
1.53 mmol), 3-hexyloxyphenylboronic acid 7 (14.70 g, tion was then heated under reflux for a further 12 h. The
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0.07 mol), potassium phosphate (28.00 g, 0.13 mol), mixture was cooled and the precipitate filtered off. The
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bis(triphenylphosphine)nickel (II) chloride (0.996 g, 1.53 crude product was purified by column chromatography
mmol) and triphenylphosphine (0.80 g, 3.04 mmol) were (eluting with dichloromethane then THF/petroleum ether
stirred in dry, refluxing toluene for 72 h under nitrogen. 1:4) and recrystallized from THF/methanol to give the
Water was added and the mixture extracted with dichlo- title compound. Yield 0.050 g (7%). Anal. calcd. for
romethane (3 × 100 mL). The solvent was removed in C128H136O8N8Zn.2H2O: C, 76.26; H, 7.00; N, 5.56%.
vacuo and the crude product purified by column chroma- Found: C, 76.35; H, 6.07; N, 5.36. UV-vis (THF): λmax,
tography (eluting with petroleum ether/dichloromethane, nm (log ε) 744 (5.53). MS (MALDI): m/z 1980. Calcd.
1:1) to give the pure title compound as a colorless oil. for [M]+ 1980.
Yield 1.12 g (9%). IR (Nujol): νmax, cm-1 2225 (CN). 1H 1-bromo-3-dodecyloxybenzene 6. The procedure
NMR (300 MHz, CDCl3, Me4Si): δH, ppm 7.86 (2 H, s), described for the synthesis of compound 5 was applied
7.20 (2 H, dd, J = 8.2, 7.6 Hz), 6.85 (2 H, d, J = 8.2 Hz), using 3-bromophenol 4 (25 g, 0.145 mol), 1-bromodode-
6.70 (2 H, d, J = 7.6 Hz), 6.64 (2 H, s), 3.78 (4 H, t, J = cane (54.20 g, 0.216 mol) and anhydrous potassium car-
6.6 Hz), 1.73–1.64 (4 H, m), 1.45–1.27 (12 H, m), 0.92 bonate (30 g, 0.43 mol). The residue was distilled under
(3 H, t, J = 6.8 Hz). 13C NMR (75.45 MHz, CDCl3, Me4Si): reduced pressure (143 °C, 1 mm.Hg) to give the pure
δC, ppm 159.4, 146.0, 139.1, 135.6, 129.9, 121.6, 115.6, title compound 47.0 g (99%). Anal. calcd. for C32H42O4:
115.4, 115.3, 114.5, 68.2, 31.6, 29.1, 25.7, 22.6, 14.1. C, 63.34; H, 8.56%. Found: C, 63.59; H, 8.61. 1H NMR
MS (EI): m/z 480. Calcd. for [M]+ 480. HRMS: calcd. for (300 MHz, CDCl3, Me4Si): δH, ppm 7.14–7.03 (3 H, m),
[M + NH4]+ 498.3121. Found: 498.3109. 6.81 (1 H, d, J = 1.1 Hz), 3.67 (2 H, t, J = 6.5 Hz), 1.78–
6,11-bis(hexyloxy)triphenylene-2,3-dicarbonitrile 1.22 (2 H, m), 1.55–1.22 (18 H, m), 0.87 (3 H, t, J =
18. (a) 6,11-bis(hexyloxy)-triphenylene-2,3-ditriflate 16 6.9 Hz). 13C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm
(0.50 g, 7.0 mmol), tris(dibenzylidene-acetone)dipalladium 159.4, 129.9, 122.9, 122.2, 117.1, 112.9, 67.6, 31.2, 28.9,
(0) (0.025 g, 0.028 mmol) and 1,1′-bis(diphenylphosphino)- 28.8, 28.7, 28.6, 28.4, 25.2, 21.9, 13.6. MS (EI): m/z 340.
ferrocene (0.062 g, 0.15 mmol) were stirred in DMF Calcd. for [M (79Br)]+ 340.
(20 mL). The temperature of the mixture was raised to 3-dodecyloxyphenylboronic acid 8. The procedure
140 °C and zinc cyanide (0.31 g, 2.61 mmol) added in small described for the synthesis of compound 7 was applied
portions over 2 h. The mixture was heated for a further using 1-bromo-3-dodecyloxy-benzene 6 (45 g, 0.132
48 h. Aqueous ammonia and ammonium chloride were mol), magnesium turnings (4.00 g, 0.584 mol) and trim-
added and the mixture extracted with dichloromethane ethylborate (30.0 g, 0.264 mol). The crude product was
(3 × 100 mL). The crude product was purified by col- recrystallized from petroleum ether to give the title com-
umn chromatography (eluting with dichloromethane/ pound. Yield 22.35 g (47%). 1H NMR (300 MHz, CDCl3,
petroleum ether, 1:1) and recrystallization from pentanol Me4Si): δH, ppm 7.82–7.74 (2 H, m), 7.12–7.45 (2 H, m),
to give the pure title compound as a white solid. Yield 4.82–4.00 (2 H, m), 1.87–1.73 (2 H, m), 1.66–1.26 (18 H,
0.080 g (23%). (b) The procedure described for com- m), 0.87 (3 H, t, J = 6.9 Hz).
pound 12 was applied using 3,3′′-bis(hexyloxy)- 3,3′′-bis(dodecyloxy)-4′,5′-dimethoxy-[1,1′;2′,1′′]-
[1,1′;2′,1′′]terphenyl-4′,5′-dicarbonitrile 40 (0.70 g, 1.45 terphenyl 11. The procedure for the synthesis of com-
mmol), dichloromethane (50 mL) and iron (III) chloride pound 10 was applied using 3-dodecyloxyphenylboronic
(0.94 g, 5.0 mmol). The crude residue was purified by acid 8 (18.26 g, 0.061 mol), 1,2-dibromo-4,5-dimethoxy-
column chromatography (eluting with dichloromethane/ benzene 9 (6.0 g, 0.020 g), sodium carbonate (10.74
petroleum ether, 1:4) and recrystallization from pentanol g, 0.10 mol), triphenylphosphine (0.32 g, 1.21 mmol)
to give the pure title compound. Yield 0.05 g (7%); mp and palladium chloride (0.11 g, 0.61 mmol). The crude

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 240–246

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 SYNTHESIS AND PROPERTIES OF MACRODISCOTIC TRIPHENYLENOPHTHALOCYANINES 241

product was purified using column chromatography from propan-2-ol to give the pure title compound. Yield
(eluting with dichloromethane/petroleum ether, 1:4) to 2.0 g (83%); mp 74 °C. Anal. calcd. for C44H58O8S2F6:
give the pure title compound as colorless crystals. Yield C, 59.18; H, 6.55%. Found: C, 59.33; H, 6.62. 1H NMR
9.86 g (74%); mp 63 °C. 1H NMR (300 MHz, CDCl3, (300 MHz, CDCl3, Me4Si): δH, ppm 8.51 (2 H, s), 8.42
Me4Si): δH, ppm 7.12 (2 H, dd, J = 8.1, 7.7 Hz), 6.95 (2 H, d, J = 9.0 Hz), 7.75 (2 H, d, J = 2.5 Hz), 7.32 (2 H,
(2 H, s), 6.75–6.67 (6 H, m), 3.94 (3 H, s), 3.74 (4 H, t, dd, J = 9.0, 2.5 Hz), 4.17 (4 H, t, J = 6.3 Hz), 1.92–1.85
J = 6.6 Hz), 1.68–1.59 (4 H, m), 1.39–1.26 (36 H, m), (4 H, m), 1.57–1.27 (36 H, m), 0.88 (6 H, t, J = 6.8 Hz).
0.88 (6 H, t, J = 6.5 Hz). 13C NMR (75.45 MHz, CDCl3, 13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 158.5,
Me4Si): δC, ppm 158.9, 148.5, 143.1, 133.2, 129.1, 122.4, 138.9, 130.9, 128.0, 124.8, 124.7, 121.1, 118.7, 118.0,
116.2, 113.7, 113.3, 68.1, 56.2, 32.0, 29.8, 29.7, 29.6, 107.2, 68.7, 31.9, 29.8, 29.7, 29.6, 29.5, 29.4, 26.1, 22.7,
29.4, 29.3, 29.2, 26.1, 22.7, 14.1. MS (EI): m/z 658. 14.1. MS (FABMS): m/z 892. Calcd. for [M]+ 892.
Calcd. for [M]+ 658. HRMS: calcd. for [M]+ 658.4961. 3,3′′-bis(dodecyloxy)-[1,1′;2′,1′′]terphenyl-4′,5′-
Found: 658.4966. dicarbonitrile 41. The procedure described for the
6,11-bis(dodecyloxy)-2,3-dimethoxytriphenylene synthesis of compound 40 was applied using 4,5-dichlo-
13. The procedure described for the synthesis of com- rophthalonitrile 39 (1.00 g, 5.08 mmol), 3-dodecyloxy-
pound 12 was applied using 3,3′′-bis(dodecyloxy)-4′,5′- phenylboronic acid 8 (4.00 g, 0.014 mol), potassium
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

dimethoxy-[1,1′;2′,1′′]terphenyl 11 (4.37 g, 6.64 mmol) phosphate (5.70 g, 0.026 mol), bis(triphenylphosphine)-

by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

and iron (III) chloride (3.00 g, 0.0192 mol). The crude nickel (II) chloride (0.20 g, 0.31 mmol) and triph-
product was purified by column chromatography (eluting enylphosphine (0.16 g, 0.61 mmol). The crude product
with dichloromethane/petroleum ether, 1:4) and recrys- was purified by column chromatography (eluting with
tallization from propan-2-ol to give pure title compound. petroleum ether/dichloromethane, 1:1) to give the pure
Yield 2.35 g (54%); mp 113 °C. Anal. calcd. for C44H64O4: title compound as a colorless oil. Yield 0.16 g (5%).
C, 80.44; H, 9.82%. Found: C, 80.38; H, 9.86. 1H NMR IR (Nujol): νmax, cm-1 2225 (CN). 1H NMR (300 MHz,
(300 MHz, CDCl3, Me4Si): δH, ppm 8.45 (2 H, d, J = CDCl3, Me4Si): δH, ppm 7.84 (2 H, s), 7.18 (2 H, dd, J =
9.1 Hz), 7.87 (2 H, s), 7.85 (2 H, d, J = 2.3 Hz), 7.21 (2 8.3, 7.8 Hz), 6.83 (2 H, dd, J = 8.3, 2.3 Hz), 6.68 (2 H,
H, dd, J = 9.1, 2.3 Hz), 4.19–4.11 (10 H, m), 1.92–1.85 d, J = 7.8 Hz), 6.62 (2 H, d, J = 2.3 Hz), 3.76 (4 H, t, J =
(4 H, m), 1.57–1.27 (36 H, m), 0.87 (6 H, t, J = 7.7 Hz). 6.5 Hz), 1.72–1.62 (4 H, m), 1.54–1.27 (m, 36 H), 0.87 (6
13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 157.9, H, t, J = 6.8 Hz). 13C NMR (75.45 MHz, CDCl3, Me4Si):
149.7, 130.1, 124.6, 123.6, 114.8, 107.2, 104.9, 68.5, δC, ppm 158.6, 145.2, 138.3, 134.8, 129.1, 120.8, 114.8,
56.1, 31.9, 29.7, 29.6, 29.5, 29.4, 26.2, 22.7, 14.1. MS 114.6, 114.5, 113.7, 67.4, 31.2, 28.9, 28.8, 28.7, 28.6,
(EI): m/z 656. Calcd. for [M]+ 656. 28.3, 25.2, 21.9, 13.3. MS (FABMS): m/z 649. Calcd.
6,11-bis(dodecyloxy)-2,3-dihydroxytriphenylene for [M]+ 649. HRMS: calcd. for [M + NH4]+ 666.4999.
15. The procedure described for the synthesis of com- Found: 666.5006.
pound 14 was applied using butyllithium (2.5 M, 6,11-bis(dodecyloxy)triphenylene-2,3-dicarbo-
25.8 mL, 0.065 mol), diphenylphosphine (8.0 mL, nitrile 19. (a) The procedure described for the synthesis
0.043 mol) and 6,11-bis(dodecyloxy)-2,3-dimethoxytri- of compound 18 was applied using tris(di-benzylide-
phenylene 13 (4.0 g, 6.09 mmol). The crude product was neacetone)dipalladium (0.126 g, 0.14 mmol), 1,1′-bis-
purified by column chromatography (eluting with ethyl (diphenylphosphino)ferrocene (0.306 g, 0.55 mmol),
acetate/petroleum ether, 1:4) to give the title compound. 6,11-dihexyloxytriphenylene-2,3-ditriflate 17 (2.5 g,
Yield 1.37 g (36%). 1H NMR (300 MHz, CDCl3, Me4Si): 3.45 mmol) and zinc cyanide (0.5 g, 4.14 mmol). Puri-
δH, ppm 8.40 (2H, d, J = 8.9 Hz), 7.95 (2 H, s), 7.77 (2 H, fication was achieved by column chromatography (elut-
d, J = 2.4 Hz), 7.17 (2 H, dd, J = 8.9, 2.4 Hz), 4.13 (4 H, ing with dichloromethane/petroleum ether, 1:1) and
t, J = 6.4 Hz), 1.88–1.83 (4 H, m), 1.26–1.51 (36 H, m), recrystallization from pentanol to give the pure title
0.87 (6 H ,t, J = 6.9 Hz). 13C NMR (75.45 MHz, CDCl3, compound. Yield 80 mg (23%). (b) The procedure
Me4Si): δC, ppm 157.8, 144.3, 129.9, 125.2, 124.5, described for the synthesis of compound 12 was applied
123.5, 115.7, 109.0, 106.4, 68.4, 32.0, 29.8, 29.7, 29.6, using 3,3′′-bis(dodecyloxy)-[1,1′;2′,1′′]terphenyl-4′,5′-
29.5, 29.4, 26.2, 22.8, 14.1. MS (EI): m/z 628. Calcd. dicarbonitrile 41 (0.15 g, 0.23 mmol), dichloromethane
for [M]+ 628. HRMS: calcd. for [M]+ 629.4570. Found: (50 mL) and iron (III) chloride (0.50 g, 3.07 mmol). The
629.4569. crude product was purified by column chromatography
6,11-bis(dodecyloxy)triphenylene-2,3-ditriflate (eluting with dichloromethane/petroleum ether, 1:1) and
17. The procedure described for the synthesis of com- recrystallization from pentanol to give pure title com-
pound 16 was applied using 6,11-bis(dodecyloxy)-2,3- pound. Yield 5 mg (3%), mp 230 °C. IR (Nujol): νmax, cm-1
dihydroxytriphenylene 15 (1.70 g, 2.70 mmol), pyridine 2233 (CN). Anal. calcd. for C44H58O2N2: C, 81.68; H,
(1.75 g, 0.021 mol) and trifluoromethanesulphonic acid 9.04; N 4.33%. Found: C, 81.28; H, 8.90; N 4.15. 1H NMR
anhydride (1.83 g, 6.45 mmol). The crude product was (400 MHz, CDCl3, Me4Si): δH, ppm 8.78 (2 H, s), 8.46 (2
purified by column chromatography (eluting with dichlo- H, d, J = 9.0 Hz), 7.78 (2 H, d, J = 2.5 Hz), 7.33 (2 H, dd,
romethane/petroleum ether, 1:4) and recrystallization J = 9.0, 2.5 Hz), 4.20 (4 H, t, J = 6.5 Hz), 1.97–1.89

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 241–246

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 242 A. N. CAMMIDGE AND H. GOPEE

(4 H, m), 1.78–1.28 (36 H, m), 0.89 (6 H, t, J = 6.8 Hz). 200 mL) under nitrogen for 24 h. Water was added and the
13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 158.8, mixture extracted with dichloromethane (3 × 150 mL).
132.8, 130.2, 127.5, 125.4, 124.9, 119.8, 116.4, 111.9, The solvent was removed in vacuo to leave a dark-brown
106.7, 68.7, 32.0, 29.8, 29.7, 29.6, 29.5, 29.4, 26.2, 22.7, oil which was purified by column chromatography (elut-
14.1. MS (EI): m/z 647. Calcd. for [M]+ 647. ing with dichloromethane/petroleum ether, 1:4) to give
Octa(dodecyloxy)triphenylenophthalocyanine 21. the pure title compound as a colorless oil. Yield 5.73 g
The procedure described for the synthesis of compound (70%). Anal. calcd. for C32H42O4: C, 78.36; H, 8.57%.
20 was applied using 6,11-bis(dodecyloxy)-triphenylene- Found: C, 78.16; H, 8.72. 1H NMR (300 MHz, CDCl3,
2,3-dicarbonitrile 19 (0.30 g, 0.46 mmol), DBU (0.04 g, Me4Si): δH, ppm 7.04 (4 H, d, J = 8.8 Hz), 6.90 (2 H, s),
0.33 mmol) and zinc acetate (0.04 g, 0.19 mmol). The 6.76 (4 H, d, J = 8.8 Hz), 3.95–3.90 (10 H, m), 1.79–1.74
crude product was purified by column chromatography (4 H, m), 1.55–1.26 (12 H, m), 0.90 (6 H, t, J = 6.8 Hz). 13C
(eluting with dichloromethane then THF/petroleum ether NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 157.9, 148.2,
1:4) and recrystallized from ethyl acetate to give the title 134.1, 132.9, 131.1, 114.2, 113.9, 68.1, 56.2, 31.7, 29.4,
compound. Yield 0.01 g (3%). UV-vis (THF): λmax, nm 25.8, 22.7, 14.1. MS (EI): m/z 490. Calcd. for [M]+ 490.
(log ε) 745 (4.69). MS (MALDI): m/z 2653. Calcd. for 7,10-bis(hexyloxy)-2,3- dimethoxytriphenylene 29.
[M]+ 2653. Iodine (2.00 g, 0.004 mol) and 4,4′′-bis(hexyloxy)-4′,5′-
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

1-bromo-4-hexyloxybenzene 23. 4-bromophenol 22 dimethoxy[1,1′,2′,1′′]-terphenyl 27 (1.00 g, 0.004 mol)

by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

(50 g, 0.29 mol), 1-bromohexane (71.6 g, 0.43 mol) and were dissolved in benzene (250 mL) and the solution irra-
anhydrous potassium carbonate (60 g, 0.43 mol) were diated with UV light (125 W) for 96 h. A solution of 20%
heated in refluxing ethanol (250 mL) under nitrogen for sodium metabisulphite was added and mixture extracted
24 h. The solution was filtered, dilute hydrochloric acid with dichloromethane (3 × 150 mL). The solvent was
was added to the filtrate and the mixture extracted with evaporated and the residue purified by column chroma-
ethyl acetate (3 × 150 mL). The solvent was removed in tography (eluting with petroleum ether/dichloromethane,
vacuo and the residue distilled under reduced pressure 4:1) and recrystallization from ethanol to give the pure
(123 °C, 1 mm.Hg) to give the pure title compound. Yield title compound as colorless crystals. Yield 1.15 g (58%);
72.45 g (98%). 1H NMR (300 MHz, CDCl3, Me4Si): δH, mp 98 °C. Anal. calcd. for C32H40O4: C, 78.69; H, 8.20%.
ppm 7.36 (2 H, d, J = 9.0 Hz), 6.77 (2 H, d, J = 9.0 Hz), Found: C, 78.42; H, 8.18. 1H NMR (300 MHz, CDCl3,
3.91 (2 H, t, J = 6.4 Hz), 1.78–1.71 (2 H, m), 1.46–1.30 Me4Si): δH, ppm 8.41 (2 H, d, J = 9.0 Hz), 7.97 (2 H,
(6 H, m), 0.91 (3 H, t, J = 6.4 Hz). 13C NMR (75.45 MHz, d, J = 2.5 Hz), 7.89 (2 H, s), 7.27 (2 H, dd, J = 9.0, 2.5
CDCl3, Me4Si): δC, ppm 153.3, 132.4, 116.3, 112.5, 68.2, Hz), 4.19 (4 H, t, J = 6.4 Hz), 4.11 (6 H, s), 1.93–1.85
31.4, 28.9, 25.5, 22.4, 13.8. (4 H, m), 1.55–1.25 (12 H, m), 0.94 (6 H, t, J = 6.8 Hz).
4-hexyloxyphenylboronic acid 25. 1-bromo-4-hexy- 13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 157.9,
loxybenzene 23 (50 g, 0.195 mol) was added dropwise to 149.1, 130.5, 124.5, 124.1, 123.4, 116.2, 107.2, 104.4,
a suspension of magnesium turnings (4.74 g, 0.195 mol) 68.5, 56.1, 31.7, 29.5, 25.9, 22.7, 14.1. MS (EI): m/z 488.
in THF (150 mL) under nitrogen so as to maintain gentle Calcd. for [M]+ 488.
reflux of the THF. After addition, the reaction mixture was 7,10-bis(hexyloxy)triphenylene-2,3-diol 31. Diphe-
further refluxed for 3 h. The Grignard reagent was cooled nylphosphine (1.0 mL, 5.78 mmol) was stirred in THF (30
down to room temperature and transferred to a solution mL) under nitrogen at 0 °C. Cold butyllithium (2.5 M, 3
of trimethylborate (40.5 g, 0.39 mol) in THF (150 mL) mL, 6.4 mmol) was slowly added and the mixture allowed
at -78 °C. The reaction mixture was then allowed to to warm to room temperature. 7,10-bis(hexyloxy)-2,3-
warm up to room temperature overnight. Dilute hydro- dimethoxytriphenylene 29 (1.0 g, 2.0 mmol) was added
chloric acid (300 mL, 1 M) was added and the mix- and the mixture stirred at room temperature for 24 h.
ture extracted with diethylether (3 × 150 mL). The Dilute sulfuric acid was carefully added and the mixture
organic extracts were dried over MgSO4 and the solvent extracted with ethyl acetate (4 × 150 mL). The solvent
removed under reduced pressure. The solid was recrystal- was evaporated and the crude product purified by column
lized from petroleum ether to give pure title compound. chromatography (eluting with ethyl acetate/petroleum
Yield 25.86 g (60%); mp 92 °C. 1H NMR (300 MHz, CDCl3, ether, 1:4) to give the pure title compound as a white
Me4Si): δH, ppm 8.16 (2 H, d, J = 8.4 Hz), 7.01 (2 H, d, solid. Yield 0.70 g (75%); mp 106–110 °C. 1H NMR (300
J = 8.4 Hz), 4.06 (2 H, t, J = 6.5 Hz), 1.85–1.80 (2 H, m), MHz, CDCl3, Me4Si): δH, ppm 8.31 (2 H, d, J = 9.1 Hz),
1.55–1.35 (6 H, m), 0.90 (3 H, t, J = 7.0 Hz). 7.94 (2 H, s), 7.93 (2 H, d, J = 2.6 Hz), 7.16 (2 H, dd,
4,4′′-bis(hexyloxy)-4′,5′-dimethoxy[1,1′,2′,1′′]- J = 9.1, 2.6 Hz), 4.10 (4 H, t, J = 6.6 Hz), 1.93–1.84 (4
terphenyl 27. 4-hexyloxyphenylboronic acid 25 (11.18 g, H, m), 1.57–1.26 (12 H, m), 0.95 (6 H, t, J = 6.7 Hz).
0.051 mol), 1,2-dibromo-4,5-dimethoxybenzene (5.0 g, 13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 157.8,
0.017 mol), sodium carbonate (8.05 g, 0.08 mol), tri- 144.4, 129.9, 125.1, 124.4, 123.5, 115.7, 109.1, 106.3,
phenylphosphine (0.30 g, 1.014 mmol) and palladium 68.4, 31.7, 29.5, 25.8, 22.7, 14.1.
chloride (0.09 g, 0.51 mmol) were stirred in a refluxing 7,10-bis(hexyloxy)triphenylene-2,3-ditriflate 33. 7,10-
mixture of toluene, ethanol and water (3:3:1 respectively, bis(hexyloxy)triphenylene-2,3-diol 31 (0.70 g, 0.97 mmol)

Copyright © 2009 World Scientific Publishing Company J. Porphyrins Phthalocyanines 2009; 13: 242–246

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 SYNTHESIS AND PROPERTIES OF MACRODISCOTIC TRIPHENYLENOPHTHALOCYANINES 243

was added to dry dichloromethane (50 mL) and pyridine Found: C, 76.58; H, 6.82 N, 5.47. UV-vis (THF): λmax,
(0.70 mL, 8.0 mmol) at -20 °C. Trifluoromethanesul- nm (log ε) 747 (5.55). MS (MALDI): m/z 1979. Calcd.
phonic acid anhydride (2.4 mL, 15 mmol) was slowly for [M]+ 1979.
added to the solution and the mixture allowed to warm 1-bromo-4-dodecyloxybenzene 24. The procedure
to room temperature overnight. Dilute hydrochloric described for the synthesis of compound 23 was applied
acid was added and the mixture extracted with dichlo- using 4-bromophenol 22 (100 g, 0.58 mol), 1-bromodo-
romethane (3 × 150 mL). The solvent was removed in decane (215 g, 0.86 mol) and anhydrous potassium car-
vacuo and the residue purified by column chromatogra- bonate (120 g, 0.86 mol). The crude product was distilled
phy (eluting with dichloromethane/petroleum ether, 1:4) under reduced pressure (104 °C, 0.3 mmHg) to obtain
and recrystallization from ethanol to give the pure title the pure title compound. Yield 190.0 g (96%); mp 38 °C.
compound. Yield 0.75 g (68%); mp 114 °C. Anal. calcd. Anal. calcd. for C18H29OBr: C, 63.34; H, 8.56%. Found:
for C32H34O8S2F6: C, 53.03; H, 4.72%. Found: C, 53.29; C, 63.35; H, 8.54. 1H NMR (300 MHz, CDCl3, Me4Si):
H, 4.76. 1H NMR (300 MHz, CDCl3, Me4Si): δH, ppm δH, ppm 7.35 (2 H, d, J = 9.1 Hz), 6.76 (2 H, d, J = 9.1
8.45 (2 H, s), 8.33 (2 H, d, J = 9.2 Hz), 7.90 (2 H, d, J = Hz), 3.90 (2 H, t, J = 6.4 Hz), 1.81–1.71 (2 H, m), 1.56–
2.5 Hz), 7.30 (2 H, dd, J = 9.2, 2.5 Hz), 4.20 (4 H, t, J = 1.38 (18 H, m), 0.92 (3 H, t, J = 6.7 Hz). 13C NMR (75.45
6.4 Hz), 1.93–1.86 (4 H, m), 1.59–1.36 (12 H, m), 0.94 MHz, CDCl3, Me4Si): δC, ppm 158.6, 132.4, 116.5, 68.4,
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

(6 H, t, J = 6.8 Hz). 13C NMR (75.45 MHz, CDCl3, 31.9, 29.8, 29.7, 29.6, 29.4, 29.3, 29.2, 26.1, 22.7, 14.2.
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

Me4Si): δC, ppm 160.0, 138.3, 132.1, 129.8, 125.6, 121.8, MS (EI): m/z 340. Calcd. for [M (79Br)]+ 340.
117.8, 116.9, 107.5, 68.6, 60.0, 31.7, 29.4, 25.9, 22.7, 4-dodecyloxyphenyl boronic acid 26. The procedure
14.9. MS (CI): m/z 742. Calcd. for [M + NH3]+ 742. described for the synthesis of compound 25 was applied
7,10-bis(hexyloxy)triphenylene-2,3-dicarbonitrile using 1-bromo-4-dodecyloxybenzene 24 (120 g, 0.35
35. 7,10-bis(hexyloxy)triphenylene-2,3-ditriflate 33 (0.50 g, mol), magnesium turnings (10.13 g, 0.42 mol) and trim-
6.90 mmol), tris(dibenzylidene-acetone)dipalladium (0) ethylborate (73 g, 0.70 mol). The crude solid was then
(0.03 g, 0.027 mmol) and 1,1′-bis(diphenylphosphino)- recrystallized from petroleum ether to give the title com-
ferrocene (0.07 g, 0.11 mmol) were stirred in DMF (20 pound. Yield 71.0 g (66%). 1H NMR (300 MHz, CDCl3,
mL). The temperature of the mixture was raised to 140 °C Me4Si): δH, ppm 8.15 (2 H, d, J = 8.5 Hz), 7.00 (2 H, d,
and zinc cyanide (0.10 g, 0.82 mmol) added in small J = 8.5 Hz), 4.04 (2 H, t, J = 6.6 Hz), 1.84–1.76 (2 H, m),
portions over 2 h. The mixture was heated for a further 1.60–1.10 (18 H, m), 0.87 (3 H, t, J = 7.2 Hz).
48 h. Aqueous ammonia and ammonium chloride were 4,4′′-bis(dodecyloxy)-4′,5′-dimethoxy-[1,1′;2′,1′′]-
added and the mixture extracted with dichloromethane terphenyl 28. The procedure described for the synthesis
(3 × 100 mL). The crude product was purified by col- of compound 27 was applied using 4-dodecyloxyphe-
umn chromatography (eluting with dichloromethane/ nylboronic acid 26 (31.0 g, 0.103 mol), 1,2-dibromo-4,
petroleum ether, 1:1) and recrystallization from pentanol 5-dimethoxybenzene 9 (10.0 g, 0.034 mol), sodium car-
to give the pure title compound as a white solid. Yield bonate (20.0 g, 0.11 mol), triphenylphosphine (0.50 g,
0.092 g (28%); mp 273 °C. IR (Nujol): νmax, cm-1 2229 2.03 mmol) and palladium chloride (0.20 g, 1.01 mmol).
(CN). Anal. calcd. for C32H34N2O2: C, 80.30; H, 7.16; N, The crude product was purified by column chromatogra-
5.85%. Found: C, 80.12; H, 7.11; N, 5.76. 1H NMR (300 phy (eluting with dichloromethane/petroleum ether, 1:4)
MHz, CDCl3, Me4Si): δH, ppm 8.79 (2 H, s), 8.43 (2 H, to give the pure title compound as colorless crystals. Yield
d, J = 9.2 Hz), 7.94 (2 H, d, J = 2.5 Hz), 7.35 (2 H, dd, 16.90 g (76%); mp 70 °C. Anal. calcd. for C44H66O4: C,
J = 9.2, 2.5 Hz), 4.23 (4 H, t, J = 6.4 Hz), 1.95–1.89 80.19; H, 10.09%. Found: C, 79.90; H, 9.99. 1H NMR
(4 H, m), 1.55–1.26 (12 H, m), 0.91 (6 H, t, J = 6.8 Hz). (300 MHz, CDCl3, Me4Si): δH, ppm 7.04 (4 H, d, J = 8.8
13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 160.8, Hz), 6.89 (2 H, s), 6.75 (4 H, d, J = 8.8 Hz), 3.98–3.85
132.8, 131.7, 129.3, 125.9, 121.2, 117.2, 116.6, 111.0, (10 H, m), 1.79–1.73 (4 H, m), 1.44–1.27 (36 H, m),
107.5, 68.7, 31.7, 29.3, 25.8, 22.7, 14.1. MS (EI): m/z 0.88 (6 H, t, J = 6.8 Hz). 13C NMR (75.45 MHz, CDCl3,
478. Calcd. for [M]+ 478. Me4Si): δC, ppm 157.8, 148.0, 133.9, 132.7, 130.9, 114.0,
Octa(hexyloxy)triphenylenophthalocyanine 37. 7,10- 113.7, 67.9, 55.9, 31.8, 29.6, 29.5, 29.4, 29.3, 29.2, 25.9,
bis(hexyloxy)triphenylene-2,3-dicarbonitrile 35 (0.80 g, 22.6, 13.9. MS (FABMS): m/z 658. Calcd. for [M]+ 658.
1.67 mmol) was dissolved in 1-hexanol and DBU (0.18 g, 7,10-bis(dodecyloxy)-2,3-dimethoxytriphenylene 30.
1.17 mmol) added. The solution was refluxed for 1 h and 4,4′′-bis(dodecyloxy)-4′,5′-dimethoxy-[1,1′;2′,1′′]-terphenyl
zinc acetate (0.10 g, 0.42 mmol) added. The solution was 28 (8.60 g, 0.013 mol) was dissolved in dichloromethane
then heated under reflux for a further 12 h. The mixture (200 mL) and a solution of iron (III) chloride (3.20 g,
was cooled and the precipitate filtered off. The crude 0.0196 mol) in nitromethane (5 mL) was slowly added. The
product was purified by column chromatography (eluting mixture was stirred at room temperature for 2 h, methanol
with dichloromethane then THF/petroleum ether 1:4) and and water added and the mixture extracted with dichlo-
recrystallized from THF/methanol to give the title com- romethane (3 × 100 mL). The solvents were removed in
pound. Yield 0.038 g (5%); mp > 300 °C. Anal. calcd. vacuo and the crude product purified by column chroma-
for C128H136O8N8Zn.H2O: C, 76.95; H, 6.96; N, 5.61%. tography (eluting with dichloromethane/petroleum ether,

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 244 A. N. CAMMIDGE AND H. GOPEE

1:4) and recrystallization from propan-2-ol to give the pure (2 H, s), 8.31 (2 H, d, J = 9.3 Hz), 7.88 (2 H, d, J = 2.5
title compound. Yield 6.25 g (73%); mp 100 °C. Anal. Hz), 7.31 (2 H, dd, J = 9.3, 2.5 Hz), 4.22 (4 H, t, J = 6.6
calcd. for C44H64O4: C, 80.44; H, 9.82%. Found: C, 80.47; Hz), 1.97–1.89 (4 H, m), 1.60–1.27 (36 H, m), 0.89 (6 H,
H, 9.75. 1H NMR (270 MHz, CDCl3, Me4Si): δH, ppm 8.37 t, J = 6.5 Hz). 13C NMR (100.50 MHz, CDCl3, Me4Si):
(2 H, d, J = 9.1 Hz), 7.94 (2 H, d, J = 2.3 Hz), 7.85 (2 H, δC, ppm 160.6, 132.4, 131.0, 128.6, 125.6, 120.7, 117.2,
s), 7.25 (2 H, dd, J = 9.1, 2.3 Hz), 4.19–4.09 (10 H, m), 116.4, 110.6, 109.9, 106.9, 68.7, 32.1, 29.9, 29.8, 29.7,
1.92–1.89 (4 H, m), 1.57–1.27 (36 H, m), 0.89 (6 H, t, J = 29.6, 26.3, 22.9. 14.4. MS (FABMS): m/z 647. Calcd.
6.7 Hz). 13C NMR (77.40 MHz, CDCl3, Me4Si): δC, ppm for [M]+ 647. HRMS: calcd. for [M]+ 646.4498. Found:
157.5, 148.6, 130.2, 124.2, 123.8, 123.0, 115.9, 106.8, 646.4494.
104.0, 68.2, 55.8, 31.8, 29.6, 29.5, 29.4, 29.3, 26.122.6, Octa(dodecyloxy)triphenylenophthalocyanine 38.
14.0. MS (EI): m/z 656. Calcd. for [M]+ 656. The procedure described for the synthesis of compound
7,10-bis(dodecyloxy)-2,3-dihydroxytriphenylene 37 was applied using 7,10-bis(dodecyloxy)-triphenylene-
32. The procedure described for the synthesis of com- 2,3-dicarbonitrile 36 (0.30 g, 0.46 mmol), DBU (0.04 g,
pound 31 was applied using diphenylphosphine (26.32 g, 0.33 mmol) and zinc acetate (0.04 g, 0.19 mmol). The
0.140 mol), butyllithium (2.5 M, 90 mL, 0.212 mol) crude product was purified by column chromatography
and 7,10-bis(dodecyloxy)-2,3-dimethoxytriphenylene 30 (eluting with dichloromethane then THF/petroleum ether
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

(13.0 g, 0.02 mol). The crude product was purified by 1:4) and recrystallized from THF/methanol to give the
by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

column chromatography (eluting with ethyl acetate/ title compound. Yield 0.008 g (2%). UV-vis (THF): λmax,
petroleum ether, 1:9) to give the pure title compound. nm (log ε) 746 (4.73). MS (MALDI): m/z 2653. Calcd.
Yield 3.70 g (30%); mp 147 °C. 1H NMR (300 MHz, for [M]+ 2653.
CDCl3, Me4Si): δH, ppm 8.31 (2 H, br), 7.94 (4 H, br), 6,7,10,11-tetrakis(hexyloxy)triphenylene-2,
7.16 (2 H, br), 4.10 (4 H, t, J = 6.6 Hz), 1.92–1.78 3-dicarbonitrile 51. 2,3-dibromo-6,7,10,11-tetrakis-
(4 H, m), 1.69–1.12 (36 H, m), 0.95 (6 H, t, J = 6.5 Hz). (hexyloxy)triphenylene 49 (3.50 g, 4.45 mmol),
MS (EI): m/z 628. Calcd. for [M]+ 628. HRMS: calcd. for tris(dibenzylideneacetone)dipalladium (0) (0.005 g,
[M]+ 628.4492. Found: 628.4491. 4.45 × 10-8 mol), 1,1′-bis(diphenylphosphino)ferrocene
7,10-bis(dodecyloxy)triphenylene-2,3-ditriflate 34. (0.006 g, 0.017 mmol) were stirred in wet DMF at 130 °C.
The procedure described for the synthesis of compound Zinc cyanide (0.63 g, 5.34 mmol) was slowly added over
33 was applied using 7,10-bis(dodecyloxy)-2,3-dihy- a period of 2 h and the solution stirred at 140 °C for
droxytriphenylene 32 (3.50 g, 5.58 mmol), pyridine (3.60 48 h. Aqueous ammonia and ammonium chloride were
g, 4.0 mL, 0.013 mol) and trifluoromethanesulphonic acid added and the mixture extracted with dichloromethane.
anhydride (3.78 g, 0.013 mol). The crude product was The crude product was purified by column chromatogra-
purified by column chromatography and recrystallization phy (eluting with dichloromethane) and recrystallization
from propan-2-ol to give the pure title compound. Yield from pentanol to give the pure title compound as a yellow
4.28 g (86%); mp 65 °C. Anal. calcd. for C44H58O8S2F6: crystals. Yield 0.50 g (18%); mp 152 °C. IR (Nujol): νmax,
C, 59.18; H, 6.55%. Found: C, 59.47; H, 6.56. 1H NMR cm-1 2225 (CN). Anal. calcd. for C44H58O4N2: C, 77.84;
(300 MHz, CDCl3, Me4Si): δH, ppm 8.47 (2 H, s), 8.34 H, 8.61; N, 4.13%. Found: C, 77.57; H, 8.67; N, 3.93. 1H
(2 H, d, J = 9.1 Hz), 7.91 (2 H, d, J = 2.5 Hz), 7.30 (2 H, NMR (300 MHz, CDCl3, Me4Si): δH, ppm 8.82 (2 H, s),
dd, J = 9.1, 2.5 Hz), 4.19 (4 H, t, J = 6.6 Hz), 1.94–1.86 7.83 (2 H, s), 7.79 (2 H, s), 4.30–4.22 (8 H, m), 1.99–1.93
(4 H, m), 1.58–1.27 (36 H, m), 0.88 (6 H, t, J = 6.6 Hz). (8 H, m), 1.62–1.39 (24 H, m), 0.91 (12 H, t, J = 6.8 Hz).
13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 159.9, 13
C NMR (75.45 MHz, CDCl3, Me4Si): δC, ppm 151.9,
138.3, 132.0, 129.7, 125.6, 121.8, 120.3, 117.8, 116.8, 150.1, 131.3, 129.6, 126.2, 121.1, 116.8, 110.3, 106.5,
107.4, 68.5, 32.0, 29.8, 29.7, 29.6, 29.4, 26.2, 22.8, 14.1. 106.3, 69.6, 31.7, 29.3, 25.8, 22.7, 14.1. MS (FABMS):
MS (FABMS): m/z 892. Calcd. for [M]+ 892. m/z 678. Calcd. for [M]+ 678.
7,10-bis(dodecyloxy)triphenylene-2,3-dicarbo- Triphenylenophthalocyanine 53. The procedure
nitrile 36. The procedure described for the synthesis of described for the synthesis of compound 20 was applied
compound 35 was applied using 7,10-bis(dodecyloxy)- using 6,7,10,11-tetrakis(hexyloxy)-triphenylene-2,3-dicar-
triphenylene-2,3-ditriflate 34 (0.50 g, 0.56 mmol), bonitrile 51 (1.00 g, 1.47 mmol), DBU (0.16 g, 1.00 mmol)
tris(dibenzylidene-acetone)dipalladium (0.021 g, 0.024 and zinc acetate (0.10 g, 0.37 mmol). The crude product was
mmol), 1,1′-bis(diphenylphosphino)ferrocene (0.05 g, purified by column chromatography (eluting with dichlo-
0.09 mmol) and zinc cyanide (0.13 g, 4.14 mmol). The romethane then THF/petroleum ether 1:4) and recrystal-
crude product was purified by column chromatography lized from ethyl acetate to give the title compound. Yield
(eluting with ethyl acetate/petroleum ether, 1:9) and 0.080 g (8%). Anal. calcd. for C176H232O16N8Zn.2CH3OH:
recrystallization from pentanol to give the pure title com- C, 75.14; H, 8.50; N, 3.94%. Found: C, 75.02; H, 8.44;
pound as a white solid. Yield 0.01 g (5%); mp 142 °C. IR N, 4.02. UV-vis (THF): λmax, nm (log ε) 765 (5.08); MS
(Nujol): νmax, cm-1 2227 (CN). Anal. calcd. for C44H58O2N2: (MALDI): m/z 2781. Calcd. for [M]+ 2781.
C, 81.69; H, 9.04; N, 4.33%. Found: C, 80.74; H, 8.95; N, 2,3,6,7-tetrakis(dodecyloxy)triphenylene 48. The
4.11. 1H NMR (400 MHz, CDCl3, Me4Si): δH, ppm 8.61 procedure described for the synthesis of compound 47

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 SYNTHESIS AND PROPERTIES OF MACRODISCOTIC TRIPHENYLENOPHTHALOCYANINES 245

was applied using 2,3,6,7-tetrahydroxytriphenylene Triphenylenophthalocyanine 54. The procedure

(10.00 g, 0.034 mol), 1-bromododecane (49.80 g, 0.20 mol) described for the synthesis of compound 53 was applied
and anhydrous potassium carbonate (27.60 g, 0.20 mol). using 6,7,10,11-tetrakis-(dodecyloxy)triphenylene-2,3-
The crude product was purified by column chromato- dicarbonitrile 52 (0.30 g, 0.30 mmol), DBU (0.03 g,
graphy (eluting with petroleum ether/dichloromethane, 0.21 mmol) and zinc acetate (0.03 g, 0.12 mmol). The
4:1) and recrystallization from propan-2-ol to give the crude product was purified by column chromatography
pure title compound as a white solid. Yield 30.75 g (eluting with dichloromethane then THF/petroleum
(93%); mp 85 °C. Anal. calcd. for C66H108O4: C, 82.10; ether 1:4) and recrystallized from ethyl acetate to give
H, 11.27%. Found: C, 81.99; H, 11.13. 1H NMR (300 the title compound. Yield 0.003 g (1%). Anal. calcd. for
MHz, CDCl3, Me4Si): δH, ppm 8.26 (2 H, dd, J = 9.9, 3.4 C272H424O16N8Zn.2EtOAc: C, 78.04; H, 10.25; N, 2.64%.
Hz), 8.02 (2 H, s), 7.84 (2H, s), 7.56 (2 H, dd, J = 9.9, 3.4 Found: C, 78.02; H, 9.99; N, 2.62. UV-vis (THF): λmax,
Hz), 4.26–4.21 (8 H, m), 1.99–1.90 (8 H, m), 1.59–1.27 nm (log ε) 764 (4.19). MS (MALDI): m/z 4129. Calcd.
(72 H, m), 0.90 (12 H, t, J = 6.7 Hz). 13C NMR (75.45 for [M]+ 4129.
MHz, CDCl3, Me4Si): δC, ppm 49.8, 149.3, 129.2, 126.2,
124.4, 123.9, 123.1, 107.3, 69.9, 69.5, 32.0, 29.8, 29.7,
29.6, 29.5, 29.4, 26.3, 22.8, 14.2. MS (FABMS): m/z 966. CONCLUSION
J. Porphyrins Phthalocyanines 2009.13:235-246. Downloaded from www.worldscientific.com

Calcd. for [M]+ 966.

by UNIVERSIDADE FEDERAL DE SAO CARLOS on 11/22/13. For personal use only.

In conclusion we have reported the synthesis and char-

2,3-dibromo-6,7,10,11-tetrakis(dodecyloxy) acterization of substituted triphenylenophthalocyanines.
triphenylene 50. The procedure described for the The materials show red-shifted absorption spectra but
synthesis of compound 49 was applied using 2,3,6,7- a strong tendency to aggregate in solution. All materi-
tetrakis(dodecyloxy)triphenylene 48 (5.00 g, 5.18 mmol) als exhibit columnar mesophases, with the long-chain
and bromine (8.30 g, 0.052 mol). The crude product was and heavily substituted derivatives showing particularly
purified by column chromatography (eluting with petro- broad ranges; in some cases the range extends from room
leum ether/dichloromethane, 4:1) and recrystallization temperature to beyond 300 °C.
from propan-2-ol to give the pure title compound. Yield
4.60 g (79%); mp 81 °C. Anal. calcd. for C66H106O4Br2: Acknowledgements
C, 70.57; H, 9.51; Br, 14.23%. Found: C, 70.20; H, 9.28;
Br, 14.38. 1H NMR (300 MHz, CDCl3, Me4Si): δH, ppm We thank UEA, CVCP (ORS award) and Dstl for
8.55 (2 H, s), 7.73 (2 H, s), 7.71 (2 H, s), 4.24–4.08 (8 H, funding and the EPSRC Mass Spectrometry Service
m), 1.97–1.90 (8 H, m), 1.57–1.27 (72 H, m), 0.89 (12 Centre at Swansea.
H, t, J = 6.7 Hz). 13C NMR (75.45 MHz, CDCl3, Me4Si):
δC, ppm 150.4, 149.6, 129.6, 127.9, 124.7, 122.0, 106.9, REFERENCES
106.8, 69.7, 69.6, 32.0, 29.8, 29.7, 29.6, 29.4, 26.3, 26.2,
22.7, 14.1. MS (FABMS): m/z 1123. Calcd. for [M (79Br, 1. a) McKeown NB. Phthalocyanine Materials: Syn-
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6,7,10,11-tetrakis(dodecyloxy)triphenylene-2, 1998. b) de la Torre G, Claessens CG and Torres T.
3-dicarbonitrile 52. The procedure described for the Chem. Commun. 2007; 2000–2015.
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mo-6,7,10,11-tetrakis(dodecyloxy)triphenylene 50 (2.25 287–289. b) Cuellar EA and Marks TJ. Inorg. Chem.
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followed by recrystallization from pentanol to give the KA. Pramana 1977; 9: 471–480. b) Cammidge AN
pure title compound as a yellow solid. Yield 0.73 g and Bushby RJ. In Handbook of Liquid Crys-
(36%); mp 175 °C. IR (Nujol): νmax, cm-1 2223 (CN). tals, Vol. 3, Demus D, Goodby J, Gray GW and
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2.76%. Found: C, 79.99; H, 10.10; N, 2.98. 1H NMR pp. 693.
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H, m), 1.59–1.12 (72 H, m), 0.88 (12 H, t, J = 6.8 Hz). Steinke N, Giesselmann F, Hagle C, Scalia G, Judele
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150.1, 131.2, 129.6, 126.1, 121.0, 116.7, 110.2, 106.5, M. Angew Chem. Int. Ed. 2007; 46: 4832–4887.
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26.1, 22.7, 14.1. MS (FABMS): m/z 1015. Calcd. for 2697–2708. b) Kumar S. Liquid Crystals 2004; 31:
[M]+ 1015. 1037–1059.

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written permission.
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