The trisubstituted-triazole approach to extended functional naphthalocyanines

Article abstract of DOI:10.1142/S1088424611003781

Recently, a novel modular approach to octatriazole-derived phthalocyanines (Pcs; 1) was developed and optimized in our group; herein, the pool of the functional Pc materials was expanded for an additional candidate (2), a fused derivative of 1. Compared w

Full text of DOI:10.1142/S1088424611003781

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2011; 15: 898–907
DOI: 10.1142/S1088424611003781
Published at http://www.worldscinet.com/jpp/
The trisubstituted-triazole approach to extended functional
naphthalocyanines
Michal Jurícˇek, Kathleen Stout, Paul H.J. Kouwer and Alan E. Rowan*
Institute for Molecules and Materials, Radboud University Nijmegen, Department of Molecular Materials,
Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands
Dedicated to Professor Karl M. Kadish on the occasion of his 65th birthday
Received 29 April 2011
Accepted 27 May 2011
ABSTRACT: Recently, a novel modular approach to octatriazole-derived phthalocyanines (Pcs; 1) was
developed and optimized in our group; herein, the pool of the functional Pc materials was expanded for
an additional candidate (2), a fused derivative of 1. Compared with 1, the aromaticity in 2 is extended
by an additional four benzene and eight triazole rings and, in addition, the triazole units and the Pc core
co-create four functional, in-plane cavities. Various methods to link the unsubstituted carbon atoms of
the neighboring triazoles in 1 to afford atomically flat naphthalocyanine (Nc) analogs (2), containing
eight fused triazole moieties, were studied. Several synthetic routes were designed, among them the
trisubstituted-triazole approach, which was found to be the most suitable route. The crucial steps of this
approach, the copper-catalyzed azide-haloalkyne cycloaddition and the intramolecular homocoupling
reactions, were first studied on a model system; subsequently, this methodology was applied in the
synthesis of the desired Nc 2. The increased core size and the π-electron deficient structure predict this
class of Ncs to possess very strong aggregation properties. Moreover, owing to the presence of four
tridentate half-cavities, the final properties of the molecule or the assembly can, in principle, be further
tuned by doping with metals or guest molecules.
KEYWORDS: conjugation, CuAHAC, homocoupling, naphthalocyanine, triazole.
arrays exhibit unique photophysical and (opto)electronic
INTRODUCTION
properties as a result of excitonic interactions between
Phthalocyanines (Pcs) [1–8] belong to a magic pool of
adjacent dye units [17]. Despite their great potential,
organic molecules that have “dyed” their way to modern
however, the synthetic methodologies leading to Pc
science and nowadays find use in various applications,
derivatives have remained, after more than 100 years,
for instance, as organic field-effect transistors [9, 10],
somewhat traditional.
optical switching and limiting devices [11, 12], sensors
In the course of our recent studies on the develop-
[9, 10], organic light-emitting devices [13], low-band-
ment of a novel modular approach to functional Pcs by
gap molecular solar cells [14, 15] and nonlinear optical
using the copper-catalyzed azide-alkyne cycloaddition
materials [11, 16]. This is due to their outstanding dye
(CuAAC) reaction [18, 19], a variety of octatriazole-
properties and the ability to self-assemble, by means of
π–π interactions, into highly ordered arrays that can be
tuned by careful design of their periphery (e.g., equipping
derived Pcs 1 (Fig. 1) with potential electronic applica-
tions was prepared [20, 21]. Using this approach, the
peripheral groups can be introduced, using mild condi-
tions, in the final step of the Pc synthesis, allowing the
them with specific molecular-recognition sites). These
introduction of more sensitive groups that are not com-
patible with harsh cyclization conditions. Additionally,
SPP full member in good standing
the ability of the resulting materials to self-assemble into
well-defined supramolecular structures upon doping with
*Correspondence to: Alan E. Rowan, email: a.rowan@science.
ru.nl, tel: +31 (0)24-36-52323, fax: +31 (0)24-36-52929
Copyright © 2011 World Scientific Publishing Company

The TrISubSTITuTeD-TrIazOle aPPrOaCh TO exTenDeD funCTIOnal naPhThalOCyanIneS
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of this new class of materials and the preliminary study
of their electronic properties.
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EXPERIMENTAL
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All chemicals and solvents were purchased from
commercial sources and used without further purifica-
tion unless stated otherwise. Solvents were distilled
prior to use: THF (Na); CH2Cl2, diisopropylethylamine
(DIPEA), 2-(dimethylamino)ethanol (DMAE), Et3N and
MeOH (CaH2). All cross-coupling and CuAHAC reac-
tions were performed under an argon atmosphere using
Schlenk techniques and deoxygenated solvents (three
freeze-pump-thaw cycles, <0.4 mbar) unless stated oth-
erwise. Silica gel (0.035–0.070 mm) from Acros or silica
gel (0.063–0.200 mm) from J. T. Baker were used for
column chromatography and silica 60 F254 coated glass
plates from Merck were used for thin-layer chromatog-
raphy (TLC).
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1
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The FT-infrared spectra were recorded on a Thermo-
Mattson IR300 spectrophotometer equipped with a Har-
rick ATR unit. The UV-vis spectra were recorded on a
Varian Cary 50 spectrophotometer. The 1H and 13C NMR
spectra were recorded on a Bruker DPX-200 instrument
(operating at 200 and 50 MHz, respectively), on a Bruker
DMX-300 instrument (operating at 300 and 75 MHz,
respectively) or on a Varian Inova 400 instrument (oper-
ating at 400 MHz (1H NMR)). All NMR spectra were
recorded at 25 °C unless stated otherwise. Chemical shifts
(δ) are reported in parts per million (ppm) relative to the
residual peak of the solvent (1H and 13C NMR, respec-
tively): CDCl3 (δ = 7.26 and 77.00 ppm) and THF-d8 (δ =
3.58 and 67.21 ppm) [27]. Multiplicities of the 1H NMR
signals are assigned as following: s (singlet), d (doublet),
t (triplet), m (multiplet), b (broad) or as a combination
(e.g., bd (broad doublet), dd (doublet of doublets), etc.).
Coupling constants are reported as a J value in Hertz (Hz).
The number of protons for a given resonance is indicated
as nH and is based on spectral integration values. The
resolution of the spectrum was increased, when neces-
sary, by performing an exponential or TRAF apodization
of the FID by using the MestReNova software. EIMS and
HRMS (EI) measurements were performed on a Micro-
mass VG7070E instrument. ESIMS measurements were
performed on a Thermo Finnigan LCQ Advantage MAX
instrument using MeOH or MeOH/THF (95/5) as the sol-
vent. HRMS (ESI) measurements were performed on a
JEOL AccuTOF-CS instrument using MeOH or MeOH/
THF (95/5) as the solvent. MALDI-TOF MS measure-
ments were performed on a Bruker BiFLEX III spectro-
meter operating in reflectron mode. All compounds were
characterized by one of the HRMS techniques, except
for compound 2b, which could only be characterized by
MALDI-TOF MS.
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Zn
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increased
core size
functional
cavity
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Fig. 1. Structures of octatriazole-derived Pc 1 and its planar Nc
analog 2; the functional cavity and the extended conjugation in
2 are highlighted in bold
metals was demonstrated [21, 22]. Apart from ligation,
the two neighboring triazole groups in 1 provide another
opportunity: to extend the π-conjugated system of the Pc.
In 1, a full planar conformation cannot be adopted due to
the steric hindrance of the triazole groups that are twisted
out of the plane of the Pc core. By linking the two triaz-
ole groups by their unsubstituted carbon atoms, a novel
planar naphthalocyanine (Nc) analog 2 (Fig. 1) can be
obtained.
A motivation for the modular synthesis of new Ncs
was their potential use as near-infrared absorbers [23–26],
since the Pc core in 2, compared with 1, is extended by
four benzene and eight triazole rings (see 2 in Fig. 1, bold).
Furthermore, the core of this molecule is atomically flat
and possesses four half-cavities, each having three nitro-
gen atoms pointing towards the center of the cavity. In
this design, the self-assembly behavior of the type 2 Ncs,
favored by the increased core size, may be tuned upon
doping (metals, guest molecules), thereby modifying the
material’s properties. Herein, we describe the synthesis
Copyright © 2011 World Scientific Publishing Company
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M. JuríCek et al.
Zn(OAc)2 was prepared by heating of the solid
Zn(OAc)2·H2Oto100°Cfor2.5hundervacuum(0.2mbar).
The residual water content was not determined and Zn(OAc)2
prepared this way was used in all experiments. Trans-di(µ-
acetato)bis[2-(di-o-tolylphosphino)benzyl]dipalladium(II)
(palladacycle catalyst) was purchased from commercial
sources. (Azidomethyl)benzene (9) [28], 1,2-diethynylbenzene
(4) [29], 1,2-diiodo-4,5-dimethoxy-benzene (14) [30], 2,3,-
9,10,16,17,23,24-octaethynylphthalocyanatozinc(II) (22)
[21], 2,3,9,10,16,17,23,24-octakis(1-dodecyl-1H-1,2,3-
triazole-4-yl)phthalocyanatozinc(II) (1) [21], 2,3,9,10,16,17,-
23,24-octakis(tert-butyldimethylsilylethynyl)
phthalocyanatozinc(II) (21) [21], triethyl 2,2′,2′′-
(4,4′,4′′-(nitrilotris(methylene))tris(1H-1,2,3-triazole-4,1-diyl))-
triacetate (10) [31] and tris((1-(tert-butyl)-1H-1,2,3-
triazol-4-yl)methyl)amine (TTTA) [32] are known from
the literature and were prepared following the described
procedures.
three times. After the addition of a mixture of Et3N and
THF (50 mL, 2/1) and trimethylsilylacetylene (6.7 mL,
47 mmol), the resulting mixture was heated to 60 °C in a
closed system under an argon atmosphere for 55 h before
it was quenched with NH4Cl (1 M). The crude product
was extracted with CH2Cl2 and the combined organic lay-
ers were dried over Na2SO4. After filtration, the solvents
were evaporated and the residue was purified by column
chromatography on silica gel using pentane/CH2Cl2 (6/1
to 1/1) to afford the pure product (6.4 g, 94%) as a white
solid. 1H NMR (300 MHz; CDCl3; Me4Si): δH, ppm 6.91
(2H, s, CArH), 3.88 (6H, s, OCH3), 0.27 (18H, s, SiCH3).
13C NMR (75 MHz; CDCl3; Me4Si): δC, ppm 149.0,
118.9, 114.4, 103.4, 96.8, 56.0, 0.1. IR (neat): νmax, cm-1
2958, 2898, 2153 (C≡C), 1597, 1506, 1449, 1392, 1344,
1273, 1249, 1219, 1204, 999, 883, 839, 758, 732. EIMS:
m/z (%) 330 ([M]+•, 100), 315 (27), 227 (17), 73 (74).
HRMS (EI): m/z calcd. for C18H26O2Si2 330.1471, found
330.1465 (|∆| = 1.9 ppm).
Synthesis of the azide and haloacetylene precursors
1,2-Diethynyl-4,5-dimethoxybenzene (16). A mixture
of 15 (5.5 g, 17 mmol), TBAF (3.3 mL, 1 M in THF), THF
(80 mL) and water (1 mL) was stirred at room temperature
for 22 h before the solvent was evaporated. The residue
was purified by column chromatography on silica gel using
pentane/CH2Cl2 (3/1 to 1/2) to afford the pure product
(2.9 g, 95%) as a light brown solid. 1H NMR (300 MHz;
CDCl3; Me4Si): δH, ppm 6.95 (2H, s, CArH), 3.88 (6H, s,
(3-Azidoprop-1-yn-1-yl)triisopropylsilane (12). A
mixture of (3-bromoprop-1-yn-1-yl)triisopropylsilane
(3.86 g, 14.0 mmol), NaN3 (1.76 g, 27.1 mmol) and
MeOH (100 mL) was heated to 75 °C for 21 h before
the solvent was evaporated and the residue was purified
by column chromatography on silica gel using pentane
to afford the pure product (3.05 g, 92%) as a colorless
13
OCH3), 3.26 (2H, s, CCH). C NMR (75 MHz; CDCl3;
1
oil. H NMR (300 MHz; CDCl3; Me4Si): δH, ppm 3.95
Me4Si): δC, ppm 149.3, 118.0, 114.7, 82.0, 79.7, 56.0.
IR (neat): νmax, cm-1 3272 (CC–H), 3250 (CC–H), 2964,
2845, 2104 (C≡C), 1595, 1509, 1437, 1384, 1341, 1261,
1215, 1091, 991, 855, 831, 719, 633. EIMS: m/z (%) 186
([M]+•, 100), 171 (21), 115 (34). HRMS (EI): m/z calcd.
for C12H10O2 186.0681, found 186.0683 (|∆| = 1.2 ppm).
1,2-Bis(iodoethynyl)-4,5-dimethoxybenzene (13).
Based on the previously described method [33]: a solu-
tion of AgNO3 (0.23 g, 1.4 mmol) in water (3 mL) was
added to a mixture of 15 (1.27 g, 6.85 mmol), NIS (3.39 g,
15.1 mmol) and acetone (100 mL). The resulting mix-
ture was stirred at room temperature in the dark for 3 h
before the solvents were evaporated. The residue was
purified by column chromatography on silica gel using
pentane/CH2Cl2 (1/1) to afford the pure product (2.1 g,
70%) as a light brown solid. 1H NMR (300 MHz; CDCl3;
Me4Si): δH, ppm 6.87 (2H, s, CArH), 3.86 (6H, s, OCH3).
13C NMR (75 MHz; CDCl3; Me4Si): δC, ppm 149.2,
119.9, 114.5, 92.4, 56.0, 8.9. IR (neat): νmax, cm-1 2963,
2927, 2845, 2164 (C≡C), 1595, 1506, 1457, 1440, 1342,
1265, 1213, 1201, 1115, 996, 911, 862, 733. EIMS: m/z
(%) 438 ([M]+•, 100), 311 (32), 98 (37). HRMS (EI): m/z
calcd. for C12H8I2O2 437.8614, found 437.8601 (|∆| =
3.0 ppm).
13
(2H, s, CH2), 1.10–1.08 (21H, m, CH(CH3)2). C NMR
(75 MHz; CDCl3; Me4Si): δC, ppm 98.5, 89.2, 40.7, 18.5,
11.1. IR (neat): νmax, cm-1 2942, 2892, 2866, 2176 (C≡C),
2123 (N3), 2070 (N3), 1463, 1335, 1240, 1024, 883. EIMS:
m/z (%) 237 ([M]+•, 30), 194 (100), 166 (36), 152 (32),
110 (39), 96 (42), 43 (42). HRMS (EI): m/z calcd. for
C12H23N3Si 237.1661, found 237.1666 (|∆| = 2.0 ppm).
1,2-Bis(iodoethynyl)benzene (8b). Based on the previ-
ously described method [33]: a solution of AgNO3 (18 mg,
0.11 mmol) in water (1 mL) was added to a mixture of 4
(67 mg, 0.53 mmol), NIS (0.26 g, 1.2 mmol) and acetone
(10 mL). The resulting mixture was stirred at room tem-
perature in the dark for 4 h before the solvents were evapo-
rated. The residue was purified by column chromatography
on silica gel using CH2Cl2 to afford the pure product (0.20 g,
1
98%) as a pale yellow oil. H NMR (400 MHz; CDCl3;
Me4Si): δH, ppm 7.46–7.34 (2H, m, AA′ of AA′BB′), 7.30–
7.19 (2H, m, BB′ of AA′BB′). 13C NMR (75 MHz; CDCl3;
Me4Si): δC, ppm 132.5, 128.3, 126.7, 92.4, 11.1. IR (neat):
ν
max, cm-1 3083, 3057, 2164 (C≡C), 1471, 1439, 1229,
1094, 1034, 949, 756. EIMS: m/z (%) 378 ([M]+•, 100),
251 (90), 124 (57), 98 (28), 74 (28). HRMS (EI): m/z calcd.
for C10H4I2 377.8403, found 377.8406 (|∆| = 0.8 ppm).
((4,5-Dimethoxy-1,2-phenylene)bis(ethyne-2,1-
diyl))bis(trimethylsilane) (15). 14 (8.0 g, 21 mmol), CuI
(0.20 g, 1.0 mmol) and Pd(PPh3)4 (0.36 g, 0.31 mmol)
were placed in a Schlenk tube equipped with a stir-
rer and the system was evacuated and filled with argon
Model studies
1,2-Bis(1-benzyl-5-iodo-1H-1,2,3-triazol-4-yl)ben-
zene (7). Based on the previously described method [32]:
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CuI (45 mg, 0.23 mmol) and 10 (0.12 g, 0.23 mmol) were
was stirred for 2 h to obtain a fine suspension of the cata-
lyst. A solution of 13 (2.0 g, 4.6 mmol) and 12 (2.4 g,
10 mmol) in THF (13 mL) was then added to the cata-
lyst mixture with a syringe and the resulting mixture was
stirred at room temperature under an argon atmosphere
in the dark for 6 d before it was quenched with aq. NH3
(10%). The crude product was extracted with CH2Cl2 and
the combined organic layers were dried over Na2SO4.
After filtration, the solvents were evaporated and the resi-
due was purified by column chromatography on silica gel
using CHCl3 and CHCl3/ethyl acetate (95/5 to 85/15) to
afford the pure product (2.6 g, 63%) as a brown solid.
1H NMR (400 MHz; CDCl3; Me4Si): δH, ppm 7.12 (2H,
s, CArH), 5.16 (4H, s, CH2), 3.94 (6H, s, OCH3), 1.05–
1.00 (42H, m, CH(CH3)2). 13C NMR (75 MHz; CDCl3;
Me4Si): δC, ppm 151.4, 149.2, 122.0, 113.8, 97.8, 89.1,
79.1, 56.0, 42.0, 18.5, 11.0. IR (neat): νmax, cm-1 2942,
2889, 2863, 2183 (C≡C), 1608, 1548, 1487, 1460, 1437,
1350, 1252, 1220, 1179, 1135, 1094, 1018, 882, 801, 733,
677, 663. HRMS (ESI): m/z calcd. for C36H54I2N6O2Si2 +
H+ 913.20144, found 913.20204 (|∆| = 0.66 ppm).
8,9-Dimethoxy-3,4-bis(3-(triisopropylsilyl)prop-2-
yn-1-yl)-3,4-dihydronaphtho[1,2-d:3,4-d′]bis([1,2,3]-
triazole) (18). Based on the previously described method
[34]: 17 (2.4 g, 2.6 mmol) and palladacycle catalyst
(12 mg, 13 µmol) were placed in a Schlenk tube equipped
with a stirrer and the system was evacuated and filled with
argon three times. After the addition of DMF (6.6 mL)
and DIPEA (0.41 g, 3.2 mmol), the system was heated
to 110 °C under an argon atmosphere for 27 h before the
solvents were evaporated. The residue was purified by
column chromatography on silica gel using CH2Cl2/ethyl
acetate (99/1 to 98/2) to afford the pure product (0.77 g,
45%) as a light brown solid. 1H NMR (400 MHz; CDCl3;
Me4Si): δH, ppm 8.16 (2H, s, CArH), 6.16 (4H, s, CH2),
4.11 (6H, s, OCH3), 0.96–0.80 (42H, m, CH(CH3)2). 13C
NMR (75 MHz; CDCl3; Me4Si): δC, ppm 150.4, 144.1,
117.73, 117.71, 103.5, 99.5, 91.4, 56.2, 41.1, 18.2, 10.7.
IR (neat): νmax, cm-1 2942, 2891, 2863, 2179 (C≡C),
1620, 1546, 1502, 1468, 1432, 1386, 1347, 1327, 1258,
1208, 1093, 1040, 1006, 886, 860, 802, 677, 666. HRMS
(ESI): m/z calcd. for C36H54N6O2Si2 + Na+ 681.37445,
found 681.37552 (|∆| = 1.58 ppm).
placed in a Schlenk tube equipped with a stirrer and the
system was evacuated and filled with argon three times.
After the addition of THF (4.5 mL), the resulting mixture
was stirred for 30 min to obtain a homogeneous solution
of the catalyst. A solution of 8b (0.41 g, 1.2 mmol) and 9
(0.35 g, 2.6 mmol) in THF (0.5 mL) was then added to the
catalyst mixture with a syringe and the resulting mixture
was stirred at room temperature under an argon atmo-
sphere in the dark for 65 h before it was quenched with
aq. NH3 (10%). The crude product was extracted with
CH2Cl2 and the combined organic layers were dried over
Na2SO4. After filtration, the solvents were evaporated and
the residue was purified by column chromatography on
silica gel using CH2Cl2 and CH2Cl2/ethyl acetate (99/1 to
94/6) to afford the pure product (0.30 g, 39%) as a white
solid. 1H NMR (400 MHz; CDCl3; Me4Si): δH, ppm 7.67–
7.60 (2H, m, AA′ of AA′BB′), 7.55–7.50 (2H, m, BB′ of
AA′BB′), 7.35–7.27 (6H, m, CArH), 7.22–7.16 (4H, m,
CArH), 5.52 (4H, s, CH2). 13C NMR (75 MHz; CDCl3;
Me4Si): δC, ppm 151.3, 134.3, 131.2, 129.8, 129.0, 128.8,
128.3, 127.7, 80.1, 54.3. IR (neat): νmax, cm-1 3061, 3031,
2240, 1603, 1495, 1452, 1332, 1217, 1133, 1076, 981,
906, 769, 725. HRMS (ESI): m/z calcd. for C24H18I2N6 +
H+ 644.97605, found 644.97655 (|∆| = 0.78 ppm).
3,4-Dibenzyl-3,4-dihydronaphtho[1,2-d-3,4-d′]-
bis([1,2,3]triazole) (3). Based on the previously described
method [34]: 7 (70 mg, 0.11 mmol) and palladacycle
catalyst (1.0 mg, 1.0 µmol) were placed in a Schlenk
tube equipped with a stirrer and the system was evacu-
ated and filled with argon three times. After the addition
of DMF (0.33 mL) and DIPEA (17 mg, 0.13 mmol), the
system was heated to 110 °C under an argon atmosphere
for 17 h before the solvents were evaporated. The resi-
due was purified by column chromatography on silica gel
using CH2Cl2/ethyl acetate (99/1 to 98/2) to afford the
1
pure product (15 mg, 36%) as a white solid. H NMR
(400 MHz; CDCl3; Me4Si): δH, ppm 8.91–8.87 (2H, m,
AA′ of AA′BB′), 7.85–7.80 (2H, m, BB′ of AA′BB′),
7.39–7.31 (6H, m, CArH), 6.88–6.82 (4H, m, CArH),
5.86 (4H, s, CH2). 13C NMR (75 MHz; CDCl3; Me4Si):
δC, ppm 144.5, 135.4, 129.6, 128.6, 128.3, 124.7, 123.5,
123.1, 119.7, 52.9. IR (neat): νmax, cm-1 3060, 3029, 2926,
2852, 1603, 1547, 1495, 1453, 1363, 1308, 1251, 1089,
990, 911, 779, 730, 690. HRMS (ESI): m/z calcd.
for C24H18N6 + H+ 391.16712, found 391.16585 (|∆| =
3.24 ppm).
3,4-Bis(3-(triisopropylsilyl)prop-2-yn-1-yl)-3,4-
dihydronaphtho[1,2-d:3,4-d′]bis([1,2,3]triazole)-8,9-
diol (19). BBr3 (0.32 mL, 3.4 mmol) was added dropwise
to a cooled solution (0 °C) of 18 (0.74 g, 1.1 mmol) in dry
CH2Cl2 (8 mL). The resulting mixture was stirred at room
temperature for 5 h under an argon atmosphere before
another portion of BBr3 (0.11 mL, 1.1 mmol) was added.
After the reaction mixture was stirred for an additional
17 h at room temperature, the reaction was quenched by
the addition of water (400 mL) and the resulting mix-
ture was saturated with NaCl. The aqueous layer was
extracted with CHCl3 (3 × 150 mL) and the combined
organic layers were washed with brine and dried over
Na2SO4. After filtration and evaporation of the solvents,
Synthesis of the octatriazole-fused naphthalocyanine
4,4′-(4,5-Dimethoxy-1,2-phenylene)bis(5-iodo-1-
(3-(triisopropylsilyl)prop-2-yn-1-yl)-1H-1,2,3-triazole)
(17). Based on the previously described method [32]: CuI
(0.17 g, 0.91 mmol) and TTTA (0.39 g, 0.91 mmol) were
placed in a Schlenk tube equipped with a stirrer and the
system was evacuated and filled with argon three times.
After the addition of THF (17 mL), the resulting mixture
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M. JuríCek et al.
the residue was dissolved in ethyl acetate (300 mL) and
successively washed with aq. NaOH (150 mL, 1 M) and
aq. HCl (150 mL, 10%) three times. The combined aq.
NaOH layers and the combined aq. HCl layers were sep-
arately extracted once with ethyl acetate (150 mL) and
the combined organic layers were subsequently washed
with aq. Na2CO3 (3 × 150 mL, sat.), aq. HCl (150 mL,
10%) and dried over Na2SO4. After filtration, the solvents
were evaporated and the crude product (0.60 g) was dried
under vacuum and used without further purification in
the next step.
3,4-Bis(3-(triisopropylsilyl)prop-2-yn-1-yl)-3,4-
dihydronaphtho[1,2-d:3,4-d′]bis([1,2,3]triazole)-8,9-
diyl bis(trifluoromethanesulfonate) (20). According to
the previously described method [35]: a solution of 19
(0.60 g, 0.95 mmol) and Et3N (0.40 mL, 2.9 mmol) in
CH2Cl2 (1 mL) was added dropwise to a cooled solu-
tion (-20 °C) of Tf2O (0.40 mL, 2.4 mmol) in CH2Cl2
(1 mL). The resulting mixture was then warmed up to
room temperature over 4 h. After stirring at room tem-
perature for an additional 16 h, the reaction mixture was
diluted with CH2Cl2 and the resulting mixture was washed
with aq. NaOH (0.25 M), aq. NH4Cl (1 M) and dried over
Na2SO4. After filtration, the solvents were evaporated and
the residue was purified by column chromatography on
silica gel using pentane/ethyl acetate (95/5 to 92/8) to
afford the product (0.45 g, 45% over the two steps start-
ing from 18) as a white solid containing approximately
5% of unknown impurities (NMR and ESIMS). 1H NMR
(400 MHz; CDCl3; Me4Si): δH, ppm 8.93 (2H, s, CArH),
6.24 (4H, s, CH2), 0.97–0.88 (42H, m, CH(CH3)2).
13C NMR (75 MHz; CDCl3; Me4Si): δC, ppm 142.9,
140.0, 123.2, 120.0, 118.7 (q, JCF = 321.0 Hz), 118.5,
98.8, 92.5, 41.5, 18.3, 10.8. IR (neat): νmax, cm-1 2945,
2892, 2866, 2180 (C≡C), 1434, 1219, 1137, 1083, 1014,
871, 818, 751, 669, 599. HRMS (ESI): m/z calcd. for
C36H48F6N6O6S2Si2 + H+ 895.25977, found 895.26224
(|∆| = 2.76 ppm).
2865, 2252 (C≡N), 2236 (C≡N), 2181 (C≡C), 1614,
1462, 1097, 1016, 906, 731, 683, 649. HRMS (ESI): m/z
calcd. for C36H48N8Si2 + H+ 649.36187, found 649.36166
(|∆| = 0.33 ppm).
23,41,113,131,203,221,293,311-Octakis(3-(triisopropylsilyl)-
prop-2-yn-1-yl)-23,41,113,131,203,221,293,311-octahydro-
octakis([1,2,3]triazolo)[4′,5′:2,3;4′′,5′′:4,5;4′′′,5′′′:11,12;
4′′′′,5′′′′:13,14; 4′′′′′,5′′′′′:20, 21; 4′′′′′′,5′′′′′′:22,23;
4′′′′′′′,5′′′′′′′:29,30; 4′′′′′′′′,5′′′′′′′′:31,32]-2,3-naphthalo-
cyanatozinc(II) (2b). A mixture of 11 (0.12 g, 0.19 mmol),
ZnCl2 (33 mg, 0.24 mmol) and DMAE (0.6 mL) was
heated to 140 °C under an argon atmosphere over 3.5 h
before the solvent was evaporated. The residue was puri-
fiedbycolumnchromatographyonsilicagelusingCH2Cl2/
isopropanol (99.5/0.5) and size-exclusion chromatogra-
phy using CH2Cl2 to afford the pure product (17 mg, 13%)
1
as a green solid. H NMR (400 MHz; CDCl3; Me4Si):
δH, ppm 10.75 (8H, s, CArH), 6.60 (16H, s, CH2), 1.21–
1.03 (m, 168H, CH(CH3)2). 13C NMR (75 MHz; CDCl3;
Me4Si): δC, ppm 154.7, 146.0, 138.4, 124.9, 120.7, 118.1,
101.5, 91.1, 42.2, 18.7, 11.9. IR (neat): νmax, cm-1 2941,
2921, 2891, 2865, 2180 (C≡C), 1729, 1613, 1552, 1460,
1353, 1257, 1128, 1097, 1060, 1014, 995, 883, 798, 769,
678, 663, 624. UV-vis (THF; c = 1.99 × 10-6 M): λmax
,
nm (log ε) 727 (5.68), 692 (4.74), 651 (4.78), 370 (5.01),
287 (5.16), 260 (5.23). UV-vis (CH2Cl2; c = 1.99 × 10-6
M): λmax, nm (log ε) 729 (5.58), 695 (4.73), 653 (4.75),
371 (5.04), 288 (5.18), 262 (5.24). MALDI-TOF MS
(2,2′:5′,2-tertiophene): m/z calcd. for C144H192N32Si8Zn
2657.35, found 2656.94.
RESULTS AND DISCUSSION
To investigate the scope and limitations of the syn-
thesis of 2 starting from a versatile octaacetylene Pc
precursor, the covalent linkage of the two carbon atoms
of the ortho-neighboring triazoles in 1 was first stud-
ied on a model system represented by compound 3. By
using extensive studies previously described in the litera-
ture, three approaches (A–C) towards the synthesis of 3
were explored (Scheme 1). In the first approach (A), the
CuAAC reaction between 1,2-diethynylbenzene (4) and
an aliphatic primary azide under air and basic conditions
(Cu[O]AAC) was investigated; a method that was pre-
viously described for an efficient formation of bistriaz-
oles [36]. In the second approach (B), bis(acetylene) 4
first underwent the standard CuAAC reaction to provide
bis(triazole) 5; subsequently, the oxidative cyclodehydro-
genation reaction [37] of system 5 was studied. In the
third approach (C), the intramolecular homocoupling
reaction of the halogen-substituted triazole-derived inter-
mediates 6 and 7, prepared by the copper-catalyzed azide-
haloalkyne cycloaddition (CuAHAC) reaction [38], was
employed. Finally, the target Nc 2 was synthesized using
the developed methodology and a basic study of its elec-
tronic properties was carried out.
3,4-Bis(3-(triisopropylsilyl)prop-2-yn-1-yl)-3,4-
dihydronaphtho[1,2-d:3,4-d′]bis([1,2,3]triazole)-8,
9-dicarbonitrile (11). This reaction was carried out in
a glove box (N2) according to the previously described
method [35]: Zn(CN)2 (47 mg, 0.40 mmol; in 20–25
equal portions over 3 h) was added to a stirred solution
of 20 (0.30 g, 0.34 mmol), Pd2(dba)3 (17 mg, 17 µmol)
and dppf (37 mg, 67 µmol) in DMF (0.85 mL) with the
temperature adjusted to 80 °C. After the resulting mix-
ture was stirred for an additional 30 min, the solvent was
evaporated and the residue was purified by column chro-
matography on silica gel using CH2Cl2/pentane (1/2 to
2/1) and CHCl3 to afford the pure product (0.15 g, 67%)
1
as a white solid. H NMR (400 MHz; CDCl3; Me4Si):
δH, ppm 9.30 (2H, s, CArH), 6.25 (4H, s, CH2), 0.91–0.80
(42H, m, CH(CH3)2). 13C NMR (75 MHz; CDCl3; Me4Si):
δC, ppm 142.4, 129.8, 124.9, 120.8, 115.3, 113.4, 98.6,
92.8, 41.6, 18.2, 10.8. IR (neat): νmax, cm-1 2944, 2922,
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903
X
[39]; the desired Nc 2a (R = C11H23), however, was not
formed and the starting material was fully recovered. This
can probably be explained by the disability of the elec-
tron deficient triazole ring to lose an electron or accept a
proton; the first steps of the two possible mechanisms of
the Scholl reaction [40, 41].
X
4
8
APPROACH A
The third attempt to synthesize 3 (approach C)
included the CuAHAC reaction of bis(haloacetylene) 8
and the subsequent intramolecular homocoupling reac-
tion of the bis(halotriazole)-derived intermediates 6 and 7
(Scheme 1). In the literature, several procedures to access
1,4,5-trisubstituted triazoles, bearing a halogen instead of
a proton in the 5-position, are described [38]; to date, the
most efficient method has been developed in the Sharpless
team [32]. This methodology employs iodoacetylenes as
starting compounds and CuI/tris((1,2,3-triazolyl)methyl)-
amine ligand as the catalytic system, and allows for an
efficient preparation of a variety of 5-iodo-1,4-disubsti-
tuted triazoles. Moreover, the three-step one-pot proce-
dure, including the iodoacetylene formation, CuAHAC
and subsequent cross-coupling reactions, proved to be
very efficient [32]. When these conditions were applied
in the synthesis of 3 starting from bis(iodoacetylene) 8b,
the desired product was formed and subsequently isolated
in 39% yield (Scheme 3).
N
N
N
R
R
N
N
N
3
APPROACH B
APPROACH C
R
X
N
N
N
R
R
N
N
N
N
N
N
N
5
N
6, 7
N
X
R
Scheme 1. Three studied approaches towards the key interme-
diate 3 (R = Ph; 6, 8a: X = Br; 7, 8b: X = I)
An efficient method for the preparation of biaryls,
using a homocoupling reaction of aryl iodides catalyzed
by a palladacycle catalyst (see the Experimental section),
was previously described in the literature [34]; however,
this methodology was not applied to the heteroaromatic
systems. Interestingly, when the intramolecular homo-
coupling reaction of bis(iodotriazole) 7 was carried out
to afford the key intermediate 3 using the described
Fusion studies on a model system
The initial studies to synthesize 3 involved all three
approaches. Approaches A and B (discussed below)
proved not to be satisfactory; preliminary studies using
approach C, however, were successful and this methodol-
ogy was applied in the synthesis of Nc 2. The first attempt
to synthesize 3 (approach A) was carried out using the
previously described method [36]. The reaction of one
equivalent of 4 with two equivalents of (azidomethyl)-
benzene (9) under air and basic conditions, however,
led to the formation of a mixture of undefined products;
only traces of compound 3 (R = Ph) were detected in one
of the fractions obtained after column chromatography
(Scheme 2). Possibly, the intermolecular homocoupling
reaction of 4, leading to oligo-/polymeric products, was
favored over the intramolecular course of the reaction.
The second attempt (approach B), employing the oxi-
dative cyclodehydrogenation reaction, was carried out
directly on a Pc system by using 1 (R = C11H23) and FeCl3
I
N
I
I
N
9
N3
N
N
N
CuI/10
N
8b
I
7, 39%
Scheme 3. Synthesis of 7 by using the CuAHAC reaction of 8b
(approach C)
I
N
N
N
N
N
N
palladacycle
catalyst
N
N
N
N
N
9
N3
DIPEA
DMF
N
N
N
7
N
Cu/CuSO4
air, K2CO3
MeCN, 25 °C
N
N
I
N
3, 35%
4
3
traces
Scheme 2. Attempt to synthesize 3 by using the Cu[O]AAC
reaction of 4 (approach A)
Scheme 4. Synthesis of the key intermediate 3 by using the
intramolecular homocoupling reaction of 7 (approach C)
Copyright © 2011 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2011; 15: 903–907

ˇ
904
M. JuríCek et al.
reaction conditions, the desired product was formed in
35% yield (Scheme 4).
CuAHAC and the homocoupling steps, were introduced
in the 4- and 5-positions of 3. Moreover, acetylene-func-
tionalized azide 12 was used in the CuAHAC step to
obtain the desired Nc 2b equipped with eight protected
acetylene groups. Octaacetylene-derived Nc 2b can be
effectively modified using the CuAAC reaction and, to
the best of our knowledge, is the first example of a new
class of versatile octaacetylene-derived Ncs (to date,
several examples of versatile acetylene-derived Pcs are
known [20, 21, 42–45]).
The synthesis of 13, the dimethoxy analog of 8b, was
carried out starting from 14 that has previously been
described in the literature [30] (Scheme 5). The Sono-
gashira cross-coupling reaction of 14 afforded intermedi-
ate 15, which after removal of the TMS groups and the
iodination reaction, afforded 13 in 63% yield over the two
steps. The CuAHAC reaction (CuI/TTTA [32]) of 13 and
the subsequent homocoupling reaction were performed
using the described conditions and afforded 18, the dime-
thoxy analog of 3, in 28% yield over the two steps. The
methyl groups in 18 were subsequently removed using the
standard BBr3 procedure [46]; pure dihydroxy intermediate
Synthesis of the fused naphthalocyanine
Once the novel route to the key intermediate 3 using
the trisubstituted-triazole route (approach C) was devel-
oped and tested on a model system, the synthesis of the
desired Nc 2 was investigated. The moderate efficiencies
of the CuAHAC and the homocoupling steps discourage
the direct preparation of 2 starting from octaacetylene-
derived Pc precursors [20, 21], which would require an
eight-fold CuAHAC step followed by a four-fold homo-
coupling step. If these do not proceed quantitatively, the
formation of a significant amount of side-products will
hamper the purification of the desired product. More-
over, the solubility restrictions of acetylene-derived Pcs
could disable the CuAHAC step. To avoid these issues,
intermediate 11, a dicarbonitrile analog of 3 and a direct
precursor of the desired Nc 2, was synthesized using
an alternative approach (Scheme 5). In this approach,
two methoxy groups, which cannot interfere with the
Si
MeO
MeO
I
I
MeO
MeO
MeO
TMSA
TBAF
CuI
Pd(PPh3)4
MeO
Si
15, 94%
16, 95%
14
NIS
AgNO3
R
I
N
N
N
12
I
I
N
N
R
R
palladacycle
catalyst
N
MeO
MeO
MeO
MeO
MeO
MeO
R
N3
N
N
DIPEA
CuI, TTTA
N
N
N
N
I
R
17, 63%
13, 70%
18, 45%
1. BBr3
2. Tf2O
N
N
N
N
N
R
R
R
N
TfO
TfO
NC
NC
Zn(CN)2
ZnCl2
DMAE
2b, 13%
Pd2(dba)3
dppf
N
N
N
N
R
N
N
11, 67%
20, 45%
R =
Si
Scheme 5. Synthetic route towards extended Nc 2b
Copyright © 2011 World Scientific Publishing Company
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The TrISubSTITuTeD-TrIazOle aPPrOaCh TO exTenDeD funCTIOnal naPhThalOCyanIneS
905
19 (see the Experimental), however, could not be iso-
lated. Presumably, the boronic ester intermediates of 19,
obtained during the aqueous work-up, induced supramo-
lecular aggregation that could only be partially broken
up under basic conditions. For this reason, crude 19 was
used in the next step to afford ditriflate 20 in 45% over-
all yield starting from 18. Finally, the cyanation reaction
of 20 using the previously described cyanation protocol
for 1,2-ditriflates [35] and subsequent cyclization using
ZnCl2/DMAE [21] were employed to afford the desired
Nc 2b.
Electronic properties
The effect of fusing four benzene and two triazole
rings to a Pc core in 2b was studied using UV-vis spec-
troscopy and by comparing the absorption maximum of
Fig. 2. UV-vis absorption spectra of Nc 2b and Pc 1 measured
in THF at 2.0 µM
Table 1. Q-band characteristics of the selected ZnPcs and
ZnNcsa
the Q-band (λmax) of 2b and selected zinc Pcs (ZnPcs)
and zinc Ncs (ZnNcs); these results are summarized in
Table 1 and Fig. 2. Four compounds (21 [21], 22 [21], 1
[21] and 2b) were investigated and compared with two
limiting cases, Pc 23 and Nc 24 [47] (both unsubstituted).
Additionally, the electronic contribution to the red shift
of the Q-band λmax of each substituent (R) relative to Pc
23 (entry 1) for every compound was calculated and the
obtained values were analyzed.
R
R
R
R
N
N
N
N
N
N
Zn
N
N
R
R
R
The values of Q-band λmax are 665 nm for Pc 23 and
756 nm for Nc 24, from which the electronic contribution
of 11 nm per half benzene ring or 22 nm per one benzene
ring can be calculated (entries 1 and 6). In this fashion, the
values of the electronic contribution were calculated for
the other compounds. As shown in Table 1, each ethynyl
group in 22 causes an additional 4.3 nm red shift (entry 3)
and each protected ethynyl group in 21, a 5.9 nm red shift
(entry 2), which is in agreement with the values previ-
ously described [48]. Interestingly, each non-conjugated
triazole moiety in 1 causes a 4.1 nm red shift that is com-
parable to that of ethynyl group (entry 4). In the case of
Nc 2b, a red shift of 7.8 nm per half benzene ring and
one triazole moiety is obtained (entry 5), which is almost
double the value compared with a non-conjugated triaz-
ole moiety (entry 4). Compared with Nc 24, however, this
value is lower despite the presence of additional eight
fused triazole rings. This is most likely due to the strong
electron-withdrawing character of the triazole moiety
possessing three nitrogen atoms in a five-membered ring.
As a result, Nc 2b represents a new class of Ncs with the
core size extended by eight five-membered rings and the
Q-band absorption maximum localized in the “stable”
region (for a comparison, all anthracocyanines (Acs)
with the core size extended by four six-membered rings
compared with Ncs are unstable, except for CoAc [25]).
These properties (increased core size and π-electron defi-
cient cloud) suggest that such structures should strongly
aggregate by means of π–π interactions.
ZnPc
R
R
R
R
R
N
R
R
R
R
R
N
Zn
N
N
N
N
N
N
R
R
R
R
R
ZnNc
R
R
Entry Type Compound
R
H
λ
max, nm nm/Rb
1
2
3
4
5
ZnPc
ZnPc
ZnPc
ZnPc
ZnNc
ZnNc
23
21
22
1
665
712
699
698
727
0
TBDMSAc
5.9
4.3
4.1
7.8
11
ethynyl
d
e
2b
24
6
a
H
756
b
UV-vis absorption spectra measured in THF. Electronic
contribution of an R substituent in nm relative to ZnPc 23
([λmax(entry) - λmax(23)]/8). (Tert-butyldimethylsilyl)ethynyl.
1-Dodecyl-1H-1,2,3-triazole-4-yl. For the structure, see
c
d
e
Fig. 1 and Scheme 5.
Copyright © 2011 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2011; 15: 905–907

ˇ
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M. JuríCek et al.
8. Phthalocyanines: Properties and Applications,
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CONCLUSION
In summary, a novel approach to a new class of atomi-
cally flat Ncs containing eight fused triazole moieties
was developed and optimized. The crucial steps of this
approach, the CuAHAC and the intramolecular homo-
coupling reactions affording the key intermediate 3, were
first studied on a model system; this methodology was
subsequently applied in the synthesis of the desired Nc
2b. In this approach, steps with good to excellent effi-
ciencies are employed and the versatility is magnified
by the possibility to postmodify the core structure of 2b
by using “click” chemistry. To approach Nc 2 modularly
starting from octaacetylene-derived Pc 22, the CuA-
HAC and homocoupling steps would have to be further
optimized to ensure they proceed quantitatively. The
increased core size and the π-electron deficient struc-
ture suggest that such a class of Ncs will possess very
strong aggregation properties; these will further be inves-
tigated. Additionally, the final properties of the molecule
or the assembly can be tuned by doping with metals or
guest molecules and by postmodification of the periph-
eral acetylene groups by using the CuAAC reaction. The
potential applications of this class of materials lie in
the construction of optoelectronic and electromagnetic
devices.
Acknowledgements
We thank the Nederlandse Organizatie voor Weten-
schappelijk Onderzoek (Netherlands Organization for
Scientific Research, NWO), NanoNed, Vici (A.E.R.),
The Council for the Chemical Sciences of the Nether-
lands Organization for Scientific Research and the Euro-
pean ITNs (CHEXTAN, SUPERIOR and HIERARCHY)
for financial support.
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