An improved protocol for the preparation of 5, 11-dialkyl-6, 12-di(hetero)aryl-5, 11-dihydroindolo[3, 2-b]carbazoles and synthesis of their new 2, 8-dicyano-/2, 8-bis(benzo[d]thiazol-2-yl)-substituted derivatives

Article abstract of DOI:10.24820/ark.5550190.p010.557

A number of 5, 11-dialkyl-6, 12-di(hetero)aryl-5, 11-dyhydroindolo[3, 2-b]carbazoles has been synthesized by modified method based on HBr catalyzed condensation of (hetero)aromatic aldehydes with indole in MeCN solution affording 5, 6, 11, 12-tetrahydroindolo[3, 2-b]carbazoles, that have been aromatized with I2 in DMF solution for 1 h at reflux, followed by alkylation of 5, 11-dihydro compounds. New 2, 8-dicyano-(10 examples) as well as 2, 8-bis(benzo[d]thiazol-2-yl)-substituted (5 examples) derivatives of these 5, 11-dyhydroindolo[3, 2-b]carbazoles have been obtained through their initial C2, 8-formylation, followed by treatment of dialdehydes with excess of hydroxylamine and dehydration of the formed aldoximes with acetic anhydride or by interaction with excess of 2-aminothiophenol in DMSO solution, respectively.

Full text of DOI:10.24820/ark.5550190.p010.557

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An improved protocol for the preparation of 5,11-dialkyl-6,12-di(hetero)aryl-
5,11-dihydroindolo[3,2-b]carbazoles and synthesis of their new 2,8-dicyano- /
2,8-bis(benzo[d]thiazol-2-yl)-substituted derivatives
Roman A. Irgashev,*a,b Nikita A. Kazin,a Gennady L. Rusinov,a,b and Valery N. Charushina,b
a Postovsky Institute of Organic Synthesis, Ural Division of the Russian Academy of Sciences, Ekaterinburg,
620990, Russia
b Ural Federal University named after the First President of Russia, B. N. Yeltsin, Ekaterinburg, 620002, Russia
Email: irgashev@ios.uran.ru
Received 03-08-2018
Accepted 04-06-2018
Published on line 06-17-2018
Abstract
A number of 5,11-dialkyl-6,12-di(hetero)aryl-5,11-dyhydroindolo[3,2-b]carbazoles has been synthesized by
modified method based on HBr catalyzed condensation of (hetero)aromatic aldehydes with indole in MeCN
solution affording 5,6,11,12-tetrahydroindolo[3,2-b]carbazoles, that have been aromatized with I2 in DMF
solution for 1 h at reflux, followed by alkylation of 5,11-dihydro compounds. New 2,8-dicyano- (10 examples)
as well as 2,8-bis(benzo[d]thiazol-2-yl)-substituted (5 examples) derivatives of these 5,11-dyhydroindolo[3,2-
b]carbazoles have been obtained through their initial C2,8-formylation, followed by treatment of dialdehydes
with excess of hydroxylamine and dehydration of the formed aldoximes with acetic anhydride or by
interaction with excess of 2-aminothiophenol in DMSO solution, respectively.
Keywords: Indolo[3,2-b]carbazole, indole, aldehydes, N-heteroacenes, benzo[d]thiazoles, nitriles
DOI: https://doi.org/10.24820/ark.5550190.p010.557
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Introduction
5,11-Dihydroindolo[3,2-b]carbazoles (indolo[3,2-b]carbazoles, ICZs) are an important class of fused nitrogen-
containing heterocycles (N-heteroarenes) with ladder-type structure, whose representatives attracted a
considerable attention of researchers thanks to their promising applications in biology1-5 and material
science.6-8 In respect to latter topic, ICZ compounds have been used as photo- and electroactive components
of organic electronic devices. In general, this is due to the fact that π-conjugated and rigid planar indolo[3,2-
b]carbazole ring system has a number of useful optical and electronic properties, as well as high thermal,
photo- and electrochemical stability as well as high resistance toward oxidation by air oxygen.9-13 Thus, a
number of ICZ derivatives, bearing (hetero)aromatic substituents at main scaffold, have been applied as
electroluminescent and charge-transport materials for organic light-emitting diodes (OLEDs)14-18 and organic
field-effect transistors (OFETs),19-22 as well as light-harvesting dyes for organic photovoltaics (OPVs).23-26 In
particular, some structures of such materials are presented in Figure 1.
Figure 1. Structures of indolo[3,2-b]carbazole-based semiconductors.
In this relation, 6,12-di(hetero)aryl-substituted indolo[3,2-b]carbazoles are of particular interest as chemical
substrates with high synthetic potential since there are wide opportunities for regioselective modification of
their structure.8 Furthermore, these ICZs are conveniently available, because they can be easily obtained by
reaction of (hetero)aromatic aldehydes with indoles in acidic conditions, followed by oxidation of intermediate
5,6,11,12-tetrahydroICZs. Thus, we have recently described a number of convenient synthetic procedures for
regioselective formylation, acylation, aroylation and nitration of 5,11-dialkyl-6,12-di(hetero)aryl-substituted
indolo[3,2-b]carbazoles at C-2 and C-8 positions, and demonstrated usefulness of the obtained functional ICZ
derivatives as building blocks for construction of more complex π-conjugated and fused molecules.27-31
Result and Discussion
In this paper, we wish to report practically improved method for preparation of 5,11-dialkyl-6,12-
di(hetero)aryl-substituted indolo[3,2-b]carbazoles, modified procedure for their formylation as well as some
new synthetic applications of the obtained 2,8-diformyl derivatives. Thus, indolo[3,2-b]carbazoles 4 can be
readily prepared in three steps through two synthetic routes (Scheme 1), which have been previously
described in the literature. In particular, 5,6,11,12-tetrahydroICZs 2 have been initially formed by
condensation of aldehydes 1 with indole in the presence of mineral acid (e.g. 57% aq. HI) on the first step.
Next, N-alkylation of compounds 2 has afforded intermediates DiAlk-2, which have further been aromatized
by treatment with DDQ in 1,4-dioxane at reflux for 5 h or with pyridinium chlorochromate (PCC) in CH2Cl2 at
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ambient temperature for 2 h, to give desired products 4.27 Thus, current way to ICZs 4 has included
aromatization step with DDQ or PCC, which are moderately toxic and not eco-friendly oxidative reagents, e.g.
PCC produced Cr-containing slugs as by-products. Compared to DDQ and PCC, the use of I2 as reagent for
aromatization of 5,6,11,12-tetrahydroICZs 2 in the alternative synthetic way to ICZs 4 is more attractive
option.32,33 However, this process requires prolonged refluxing of reaction mixture for 14 h, since compounds
2 and 3 have very poor solubility in acetonitrile (Scheme 1). Moreover, purification, including column
chromatography, of intermediates DiAlk-2 and 3 is required in both synthetic routes to ICZs 4.
Scheme 1. Synthesis of 5,11-dialkyl-6,12-di(hetero)aryl-substituted ICZs.
During our studies of 5,11-dihydroindolo[3,2-b]carbazoles, a number of valuable improvements in
preparation method of ICZs 4 have been made, since these compounds have generally been used by us as
starting ICZ substrates in our researches. Firstly, it has been found, that not only 57% aq. HI32 or equimolar
mixture of 48% aq. HBF4 and n-Bu4NI,27 but also 48% aq. HBr can catalyze condensation of indole with
aldehydes 1 to form 5,6,11,12-tetrahydroICZs 2 (Scheme 2). Moreover, current process proceeds fairly quickly,
Scheme 2. Modification in synthesis of ICZs 3 and their 5,11-dialkyl derivatives 4.
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because the main amounts of intermediates 2a-j precipitated during 2 h since the beginning of reaction, and
the further increase of the reaction time does not substantially increase yields of compounds 2. Secondly, we
have found that N,N-dimethylformamide (DMF) can be successfully used as solvent for aromatization of
intermediates 2 with I2, since these compounds have very good solubility in DMF at high temperature.
Table 1. Scope and yields of ICZs 3 and 4
Entry ICZs 3 or 4
(Het)Ar
phenyl
4-methoxyphenyl
3,4,5-trimethoxyphenyl
4-chlorophenyl
thiophen-2-yl
benzo[b]thiophen-2-yl
4-hexyloxyphenyl
4-octylphenyl
Alk
Yield (%) a
36
1
2
3
4
5
3a
3b
3c
3d
3e
3f
-
-
-
-
72
60
54
48
68
55
23
43
42
84
76
79
57
71
87
67
6
-
-
-
-
7
8
9
3g
3h
3i
4-fluorophenyl
4-isopropylphenyl
phenyl
10
11
12
13
14
15
16
17
18
19
20
3j
-
4a
4b
4c
4d
4e
4f
4g
4h
4i
n-C6H13
n-C6H13
4-methoxyphenyl
3,4,5-trimethoxyphenyl n-C6H13
4-chlorophenyl
thiophen-2-yl
phenyl
n-C6H13
n-C6H13
n-C12H25
n-C12H25
4-methoxyphenyl
3,4,5-trimethoxyphenyl n-C12H25
66
50
82
4-chlorophenyl
thiophen-2-yl
n-C12H25
n-C12H25
4j
a Yields of ICZs 3a-j based on starting aldehydes 1a-j and indole.
Thus, a series of ICZs 3 has been obtained starting from 5,6,11,12-tetrahydro derivatives 2, without
purification in the previous step, by heating their DMF solutions with I2 (1 equiv.) for 1 h at reflux (Scheme 2,
Table 1) instead of 14 h according to the known procedure with acetonitrile. Pure products 3 have been
obtained by simple filtration of cooled reaction mixtures and one more crystallization of crude samples from
DMF. It should be noted, that current procedure for preparation of ICZs 3 is fully applicable for their multigram
scale syntheses. Further alkylation of ICZ compounds 3 proceeded smoothly at their treatment with long-chain
alkyl bromides, namely 1-bromohexane and 1-bromododecane, in the presence of potassium tert-butoxide in
dry DMSO solution for 1 h, affording derivatives 4 (Table 1, entries 11-20). The latter ICZ compounds have
been used for preparation of their 2,8-diformyl-substituted derivatives by the Rieche formylation. In
particular, the treatment of ICZs 4 with commercial dichloromethyl methyl ether (3 equiv.) in the presence of
SnCl4 in dry CH2Cl2 at -20 °C for 15 min and then 1 h at room temperature was found to give dialdehydes 5 in
good yields (Scheme 3, Table 2). The current yields of dialdehydes 5b and 5e are fully comparable with the
yields obtained by our previous procedure for formylation of ICZs 4 with dichloromethyl n-pentyl ether,27 that
needed to be prepare from n-pentyl fromiate. In its turn, dialdehyde 5a has previously been obtained only via
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the double Br/Li exchange on corresponding 2,8-dibromoICZ with n-BuLi, followed by treatment of the formed
organodilithium compound with excess of dry DMF.33 In addition, monoaldehyde 6 has been synthesized by
treatment of compound 4b with stoichiometric amounts of dichloromethyl methyl ether (1 equiv.) in the same
manner. However, further formylation of 6, as unwanted reaction, has been also observed under these
conditions forming dialdehyde 5b, thereby not full conversion of starting substrate 4b has been observed.
Thus, target monoaldehyde 6 has been separated from side product 5b and starting material 4b only using
column chromatography.
Scheme 3. C2- and C2,8-formylation of ICZs 4
Table 2. Scope and yields of 2,8-diformyl-substituted ICZs 5
Entry Dialdehydes 5
(Het)Ar
phenyl
4-methoxyphenyl
Alk
n-C6H13
n-C6H13
Yield of 5 (%)
1
2
3
4
5
5a
5b
5c
5d
5e
5f
91
92
55
89
76
84
72
51
81
88
3,4,5-trimethoxyphenyl n-C6H13
4-chlorophenyl
thiophen-2-yl
phenyl
n-C6H13
n-C6H13
n-C12H25
n-C12H25
6
7
8
9
5g
5h
5i
4-methoxyphenyl
3,4,5-trimethoxyphenyl n-C12H25
4-chlorophenyl
thiophen-2-yl
n-C12H25
n-C12H25
10
5j
Taking into consideration the fact that the obtained dialdehydes 5 are of utmost interest as functional
building blocks for further construction of target structures, two novel applications of these substrates for
synthesis of ICZ-based molecules have been elaborated during this study. Thus, a series of new 2,8-dicyano-
substituted ICZs 7a-j has been obtained by treatment of dialdehydes 5a-j with excess of hydroxylamine
hydrochloride and triethylamine in DMF solution for 1 h at 100 °C, that has caused smooth formation of
corresponding aldoximes, followed by addition of acetic anhydride and heating of reaction mixture at reflux
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for 1 h, to perform dehydration of the formed aldoximes (Scheme 4, Table 3). On the one hand, introduction
of cyano-groups into structure of poly(hetero)aromatics can be useful for tuning their optical and electrical
characteristics. For instance, some cyano-substituted carbazoles have recently been regarded as effective host
materials for blue phosphorescent OLEDs (PhOLEDs)34,35 or electroluminescent materials for OLEDs.36 On the
other hand, cyano-containing compounds can be interesting as chemicals for synthesis, since CN-groups are
readily able to undergo further transformations. It should be also noted, that dinitriles 7 are the first
representatives of the CN-equipped ICZ scaffold, since there are no reports in the literature on synthesis of
any such matters to the best of our knowledge.
Scheme 4. Synthesis of 2,8-dicyano-substituted ICZ derivatives 7.
Table 3. Scope and yields of 2,8-dicyano-substituted ICZs 7
Entry
1
2
3
4
5
6
7
8
Dinitriles 7
(Het)Ar
phenyl
4-methoxyphenyl
Alk
n-C6H13
n-C6H13
Yield of 7 (%)
7a
7b
7c
7d
7e
7f
7g
7h
7i
71
73
60
83
70
80
80
83
86
70
3,4,5-trimethoxyphenyl n-C6H13
4-chlorophenyl
thiophen-2-yl
phenyl
n-C6H13
n-C6H13
n-C12H25
n-C12H25
4-methoxyphenyl
3,4,5-trimethoxyphenyl n-C12H25
9
10
4-chlorophenyl
thiophen-2-yl
n-C12H25
n-C12H25
7j
It is well known that benzo[d]thiazole is often used as a mild π-acceptor part for design of various photo-
and electroactive compounds. In particular, several examples of effective luminescent and electroluminescent
materials based on benzo[d]thiazole-indolo[3,2-b]carbazole37-39 and benzo[d]thiazole-carbazole40-42 dyads
have been recently described in the literature. In this context, dialdehydes 5 have been also used for
preparation of new symmetric 2,6,8,12-tetra(hetero)aryl-substituted ICZs, bearing benzo[d]thiazol-2-yl moiety
at C-2 and C-8 (BTICZs). Thus, substrates 5f-j have smoothly reacted with 2-aminothiophenol in DMSO solution
at 160 °C for 1 h affording compounds 8f-j (Scheme 5, Table 4). Dialdehydes 5a-e, bearing n-hexyl groups at
both nitrogen atoms of their ICZ core, have also been tested in this reaction and corresponding derivatives 8
have been formed. However, all attempts at purification and characterization of the latter species have been
fruitless, since these matters have very poor solubility in most commonly used organic solvents. Compared to
this, compounds 8f-j, supported with long n-dodecyl chains, have been easily purified by crystallization from
DMF.
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Scheme 5. Synthesis of 2,8-bis(benzo[d]thiazol-2-yl)-substituted ICZ derivatives 8.
Table 4. Scope and yields of BTICZs 8
Entry
BTICZs 8
(Het)Ar
phenyl
4-methoxyphenyl
3,4,5-trimethoxyphenyl
4-chlorophenyl
thiophen-2-yl
Yield of 8 (%)
1
2
3
4
5
8f
8g
8h
8i
83
84
80
93
91
8j
Conclusions
We have made some practical improvements for the preparation of indolo[3,2-b]carbazoles, bearing
(hetero)aromatic fragments at C-6 and C-12 and long aliphatic chains at N-5 and N-11, as well as synthesized
their new 2,8-dicyano- and 2,8-bis(benzo[d]thiazol-2-yl)-substituted derivatives through primary C2,8-
formylation of these ICZ substrates and following transformations of the obtained dialdehydes. First of all, ICZ
compounds, namely 2,8-unsubstituted, 2,8-diformyl and 2,8-dycyano derivatives, reported herein are of
interest as intermediates for further chemical developments, including design of new semiconducting
materials based on them. At the same time, firstly obtained 2,8-bis(benzo[d]thiazol-2-yl) or 2,8-dicyano ICZs
can be independently considered as potential candidates for optoelectronic applications.
Experimental Section
General. Analytical studies were carried out using equipment of the Center for Joint Use “Spectroscopy and
Analysis of Organic Compounds” at the Postovsky Institute of Organic Synthesis of the Russian Academy of
1
Sciences (Ural Division). H and 13C NMR spectra were obtained on a Bruker DRX-400 and AVANCE-500
spectrometers at ambient temperature with TMS as the internal standard. Elemental analysis was carried on a
Eurovector EA 3000 automated analyzer. Mass spectrometry was performed using a Bruker maXis Impact HD
spectrometer. Melting points were determined on Boetius combined heating stages and were not corrected.
All solvents used were dried and distilled per standard procedures. The 13С NMR spectra of indolo[3,2-
b]carbazoles 3 could not be determined due to a poor solubility of these compounds in a majority of
deuterated solvents.
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General procedure for preparation of 6,12-di(hetero)aryl-5,11-dihydroindolo[3,2-b]carbazoles (3a-j). An
appropriate (het)aromatic aldehyde 1 (0.1 mol) and indole (11.7 g, 0.1 mol) were dissolved in MeCN (150 mL)
and 48% aq. HBr (1.15 mL, 10 mmol) was added in one portion to this solution at the intense stirring, herewith
an immediate staining of the solution to deep red was observed, and precipitation of intermediate 2 was
started approximately after 15 min. The resulting mixture was stirred at room temperature for 2 h and
precipitate of 2 was filtered, washed with MeCN (4×20 mL) and dried. Crude compound 2 was dissolved in
DMF (150 mL) at 150 °C and I2 (25.4 g, 0.1 mol) was added to this solution in four portions. Then, the reaction
mixture was stirred and heated at reflux for 1h, after that it was cooled to room temperature. The obtained
precipitate was filtered and dried. Crude substance was crystallized from DMF (60-80 mL) to afford analytically
pure product 3, that was filtered, washed with warm EtOH (2×20 mL) and finally dried at 120 °C.
Benzo[b]thiophen-2-carbaldehyde 1f, 4-hexyloxybenzaldehyde 1g and 4-octylbenzaldehyde 1h and were taken
in amounts of 5 mmol for preparation of corresponding products 3f-3h. Thus, indole (590 mg, 5 mmol), 48%
aq. HBr (0.06 mL, 0.5 mmol), I2 (1.27 g, 5 mmol) and proportionally decreased volumes of solvents were used
in these experiments.
6,12-Diphenyl-5,11-dihydroindolo[3,2-b]carbazole (3a). Light-yellow powder, yield 7.42 g (36%), mp ˃ 360 °C.
1H NMR (400 MHz, DMSO-d6) δ 10.53 (s, 2H), 7.77 – 7.61 (m, 10H), 7.44 (d, J 8.1 Hz, 2H), 7.28 – 7.20 (m, 2H),
7.05 (d, J 7.9 Hz, 2H), 6.85 – 6.77 (m, 2H). ICZ 3a was previously described in the literature and its analytical
data are identical to the reported data.32
6,12-Bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (3b). Light-yellow powder, yield 16.93 g
1
(72%), mp ˃ 360 °C. H NMR (500 MHz, DMSO-d6) δ 10.46 (s, 2H), 7.60 (d, J 7.7 Hz, 4H), 7.43 (d, J 7.9 Hz, 2H),
7.30 – 7.21 (m, 6H), 7.15 (d, J 8.2 Hz, 2H), 6.83 (t, J 7.6 Hz, 2H), 3.94 (s, 6H). ICZ 3b was previously described in
the literature and its analytical data are identical to the reported data.32
6,12-Bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (3c). Yellow microcrystals, yield 17.75 g
1
(60%), mp ˃ 360 °C. H NMR (500 MHz, DMSO-d6) δ 10.60 (s, 2H), 7.47 (d, J 7.9 Hz, 2H), 7.32 – 7.24 (m, 4H),
6.94 (s, 4H), 6.90 (t, J 7.4 Hz, 2H), 3.88 (s, 6H), 3.82 (s, 12H). Anal. Calcd for C36H32N2O6: C, 73.45; H, 5.48; N,
4.76. Found: C, 73.35; H, 5.53; N, 5.01.
6,12-Bis(4-chlorophenyl)-5,11-dihydroindolo[3,2-b]carbazole (3d). Light-yellow microcrystals, yield 12.94 g
1
(54%), mp ˃ 360 °C. H NMR (400 MHz, DMSO-d6) δ 10.63 (s, 2H), 7.78 (d, J 8.4 Hz, 4H), 7.71 (d, J 8.4 Hz, 4H),
7.43 (d, J 8.0 Hz, 2H), 7.31 – 7.24 (m, 2H), 7.12 (d, J 7.7 Hz, 2H), 6.91 – 6.84 (m, 2H). Anal. Calcd for C30H18Cl2N2:
C, 75.48; H, 3.80; N, 5.87; Found: C, 75.45; H, 3.87; N, 6.03.
6,12-Di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole (3e). White powder, yield 10.1 g (48%), mp ˃ 360
°C. 1H NMR (400 MHz, DMSO-d6) δ 10.77 (s, 1H), 7.96 (dd, J 5.1, 1.1 Hz, 2H), 7.52 – 7.45 (m, 4H), 7.42 (dd, J 3.4,
1.1 Hz, 2H), 7.30 (dd, J 11.1, 4.1 Hz, 2H), 7.15 (d, J 7.9 Hz, 2H), 6.95 – 6.87 (m, 2H). ICZ 3e was previously
described in the literature and its analytical data are identical to the reported data.32
6,12-Bis(benzo[b]thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole (3f). Light-yellow powder, yield 890 mg
(68%) starting from aldehyde 1f (810 mg, 5 mmol), mp ˃ 360 °C. 1H NMR (400 MHz, DMSO-d6) δ 11.00 (s, 2H),
8.19 (d, J 7.1 Hz, 2H), 8.09 (d, J 7.2 Hz, 2H), 7.81 (s, 2H), 7.58 – 7.50 (m, 4H), 7.46 (d, J 8.0 Hz, 2H), 7.34 – 7.27
(m, 4H), 6.93 – 6.86 (m, 2H). Anal. Calcd for C34H20N2S2: C, 78.43; H, 3.87; N, 5.38; S, 12.31; Found: C, 78.44; H,
3.97; N, 5.54; S, 12.45.
6,12-Bis(4-hexyloxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (3g). Light-yellow powder, yield 840 mg
1
(55%) starting from aldehyde 1g (1.03 g, 5 mmol), mp 239-240 °C. H NMR (400 MHz, DMSO-d6) δ 10.33 (s,
2H), 7.58 (d, J 8.5 Hz, 4H), 7.45 (d, J 8.0 Hz, 2H), 7.30 – 7.22 (m, 6H), 7.18 (d, J 7.9 Hz, 2H), 6.87 – 6.80 (m, 2H),
4.17 (t, J 6.5 Hz, 4H), 1.90 – 1.81 (m, 4H), 1.59 – 1.50 (m, 4H), 1.46 – 1.36 (m, 8H), 0.95 (t, J 7.0 Hz, 6H). Anal.
Calcd for C42H40N2O4: C, 82.86; H, 7.28; N, 4.60; Found: C, 82.95; H, 7.30; N, 4.53.
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6,12-Bis(4-octylphenyl)-5,11-dihydroindolo[3,2-b]carbazole (3h). Light-yellow powder, yield 364 mg (23%)
starting from aldehyde 1h (1.09 g, 5 mmol), mp 196-197 °C. 1H NMR (400 MHz, DMSO-d6) δ 10.35 (s, 2H), 7.60
(d, J 7.9 Hz, 4H), 7.53 (d, J 8.0 Hz, 4H), 7.46 (d, J 8.0 Hz, 2H), 7.24 (t, J 7.6 Hz, 2H), 7.09 (d, J 7.9 Hz, 2H), 6.79 (t, J
7.5 Hz, 2H), 2.83 (t, J 7.5 Hz, 4H), 1.86 – 1.74 (m, 4H), 1.54 – 1.25 (m, 20H), 1.00 – 0.80 (m, 6H). Anal. Calcd for
C46H52N2: C, 87.29; H, 8.28; N, 4.43; Found: C, 87.47; H, 8.45; N, 4.43.
6,12-Bis(4-fluorophenyl)-5,11-dihydroindolo[3,2-b]carbazole (3i). Light-yellow powder, yield 9.56 g (43%), mp
˃ 360 °C. 1H NMR (400 MHz, DMSO-d6) δ 10.58 (s, 2H), 7.75 – 7.68 (m, 4H), 7.59 – 7.51 (m, 4H), 7.43 (d, J 8.1
Hz, 2H), 7.29 – 7.23 (m, 2H), 7.07 (d, J 7.9 Hz, 2H), 6.89 – 6.82 (m, 2H). Anal. Calcd for C30H18F2N2: C, 81.07; H,
4.08; N, 6.30; Found: C, 81.28; H, 4.20; N, 6.35.
6,12-Bis(4-isopropylphenyl)-5,11-dihydroindolo[3,2-b]carbazole (3j). Light-yellow powder, yield 10.35 g
1
(42%), mp ˃ 360 °C. H NMR (500 MHz, DMSO-d6) δ 10.47 (s, 2H), 7.64 – 7.56 (m, 8H), 7.45 (d, J 8.0 Hz, 2H),
7.26 – 7.20 (m, 2H), 7.08 (d, J 8.0 Hz, 2H), 6.83 – 6.77 (m, 2H), 3.13 (hept, J 6.9 Hz, 2H), 1.41 (d, J 6.9 Hz, 12H).
Anal. Calcd for C36H32N2: C, 87.77; H, 6.55; N, 5.69; Found: C, 87.76; H, 6.60; N, 5.75.
General procedure for alkylation of ICZ derivatives 3a-e. An appropriate ICZ 3 (25 mmol) was dissolved in dry
DMSO (100 mL) at heating, and then the solution was cooled to room temperature at the continuous stirring
under an argon atmosphere, to form a fine suspension of ICZ substrate. Potassium tert-butoxide (8,4 g, 75
mmol) was added to this suspension in one portion, obtaining muddy green colored solution. This solution was
dropwise treated with 1-bromohexane (10.5 mL, 75 mmol) or 1-bromododecane (18 mL, 75 mmol) and the
resulting mixture was stirred at room temperature for 1 h. After that, warm water (50 mL) was added to the
mixture and the precipitate was filtered and washed wish i-PrOH or n-BuOH (2×20 mL) to remove aliphatic
impurities. Crude material was crystallized from DMF (50-60 mL) to give analytically pure product 4, that was
filtered, washed with EtOH (2×20 mL) and then dried at 120 °C.
5,11-Dihexyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole (4a). Light-yellow crystals, yield 12.11 g
(84%), mp 203-204 °C. 1H NMR (400 MHz, C6D6) δ 7.65 – 7.57 (m, 4H), 7.36 – 7.29 (m, 8H), 7.19 (d, J 8.2 Hz,
2H), 7.02 – 6.95 (m, 4H), 3.75 – 3.69 (m, 4H), 1.49 – 1.36 (m, 4H), 1.18 – 1.07 (m, 4H), 1.03 – 0.92 (m, 4H), 0.85
– 0.73 (m, 10H). ICZ 4a was previously described in the literature and its analytical data are identical to the
reported data.33
5,11-Dihexyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (4b). Light-yellow crystals, yield
12.14 g (76%), mp 199-200 °C. 1H NMR (500 MHz, C6D6) δ 7.57 – 7.50 (m, 4H), 7.39 – 7.33 (m, 2H), 7.23 (d, J 8.1
Hz, 2H), 7.19 (d, J 7.8 Hz, 2H), 7.04 – 7.00 (m, 2H), 6.99 – 6.94 (m, 4H), 3.88 – 3.77 (m, 4H), 3.42 (s, 6H), 1.53 –
1.41 (m, 4H), 1.18 – 1.09 (m, 4H), 1.04 – 0.95 (m, 2H), 0.92 – 0.77 (m, 5H). ICZ 4b was previously described in
the literature and its analytical data are identical to the reported data.27
5,11-Dihexyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (4c). Light-yellow crystals,
yield 14.95 g (79%), mp 192-193 °C. 1H NMR (500 MHz, CDCl3) δ 7.43 – 7.37 (m, 2H), 7.33 (d, J 8.1 Hz, 2H), 6.96
– 6.89 (m, 6H), 6.81 (d, J 8.0 Hz, 2H), 4.08 (s, 6H), 3.92 – 3.84 (m, 16H), 1.69 – 1.60 (m, 4H), 1.32 – 1.24 (m, 4H),
1.24 – 1.17 (m, 4H), 1.10 – 1.02 (m, 4H), 0.89 (t, J 7.2 Hz, 6H). ICZ 4c was previously described in the literature
and its analytical data are identical to the reported data.28
6,12-Bis(4-chlorophenyl)-5,11-dihexyl-5,11-dihydroindolo[3,2-b]carbazole (4d). Light-yellow crystals, yield
1
9.2 g (57%), mp 225-226 °C. H NMR (400 MHz, CDCl3) δ 7.66 – 7.57 (m, 8H), 7.39 – 7.31 (m, 2H), 7.30 – 7.26
(m, 2H), 6.92 – 6.83 (m, 2H), 6.59 (d, J 7.9 Hz, 2H), 3.85 – 3.72 (m, 4H), 1.54 – 1.44 (m, 4H), 1.29 – 1.20 (m, 4H),
1.16 – 1.08 (m, 4H), 1.00 – 0.91 (m, 4H), 0.88 (t, J 7.2 Hz, 6H). 13C NMR (101 MHz, C6D6) δ 143.2, 137.9, 134.5,
133.0, 132.5, 129.4, 126.1, 123.6, 123.2, 122.8, 118.9, 117.4, 108.9, 44.7, 31.7, 28.9, 26.7, 22.9, 14.2. Anal.
Calcd for C42H42Cl2N2: C, 78.12; H, 6.56; N, 4.34; Found: C, 77.83; H, 6.73; N, 4.33.
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5,11-Dihexyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole (4e). Light-yellow crystals, yield
10.45 g (71%), mp 216-217 °C. 1H NMR (500 MHz, CDCl3) δ 7.68 (dd, J 5.2, 1.1 Hz, 2H), 7.40 – 7.29 (m, 8H), 6.96
– 6.89 (m, 2H), 6.65 (d, J 7.9 Hz, 2H), 1.70 – 1.59 (m, 4H), 1.31 – 1.16 (m, 8H), 1.13 – 1.03 (m, 4H), 0.87 (t, J 7.2
Hz, 6H). ICZ 4c was previously described in the literature and its analytical data are identical to the reported
data.27
5,11-Didodecyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole (4f). Light-yellow crystals, yield 16.21 g
1
(87%), mp 121-122 °C. H NMR (500 MHz, C6D6) δ 7.66 – 7.61 (m, 4H), 7.37 – 7.31 (m, 8H), 7.22 (d, J 8.2 Hz,
2H), 7.04 – 6.96 (m, 4H), 3.79 – 3.70 (m, 4H), 1.53 – 1.44 (m, 4H), 1.35 – 1.20 (m, 24H), 1.20 – 1.13 (m, 4H),
1.09 – 1.01 (m, 4H), 0.92 (t, J 6.9 Hz, 6H), 0.88 – 0.80 (m, 4H). ICZ 4f was previously described in the literature
and its analytical data are identical to the reported data.31
5,11-Didodecyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (4g). Light-yellow crystals,
1
yield 13.49 g (67%), mp 136-137 °C. H NMR (500 MHz, C6D6) δ 7.60 – 7.53 (m, 4H), 7.38 – 7.34 (m, 2H), 7.25
(d, J 8.0 Hz, 2H), 7.21 (d, J 8.0 Hz, 2H), 7.05 – 7.01 (m, 2H), 7.01 – 6.96 (m, 4H), 3.92 – 3.80 (m, 4H), 3.44 (s, 6H),
1.58 – 1.47 (m, 4H), 1.36 – 1.22 (m, 24H), 1.17 (dt, J 13.3, 6.5 Hz, 4H), 1.11 – 1.03 (m, 4H), 0.96 – 0.86 (m, 10H).
ICZ 4g was previously described in the literature and its analytical data are identical to the reported data.31
5,11-Didodecyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole (4h). Light-yellow
crystals, yield 15.27 g (66%), mp 126-127 °C. 1H NMR (500 MHz, C6D6) δ 7.42 – 7.36 (m, 4H), 7.29 (d, J 8.1 Hz,
2H), 7.04 (t, J 7.6 Hz, 2H), 6.96 (s, 4H), 4.08 (s, 6H), 3.97 – 3.89 (m, 4H), 3.39 (s, 12H), 1.66 – 1.56 (m, 4H), 1.37
– 1.17 (m, 28H), 1.16 – 1.08 (m, 4H), 1.03 – 0.95 (m, 4H), 0.95 – 0.89 (m, 6H). 13C NMR (126 MHz, C6D6) δ
154.8, 143.3, 139.3, 134.5, 133.2, 126.0, 123.9, 123.4, 123.2, 119.0, 118.8, 108.9, 107.9, 61.0, 55.8, 44.8, 32.3,
30.1, 30.1, 30.0, 29.9, 29.83, 29.76, 29.7, 27.4, 23.1, 14.3. Anal. Calcd for C60H80N2O6: C, 77.88; H, 8.71; N,
3.03; Found: C, 77.53; H, 8.78; N, 3.07.
6,12-Bis(4-chlorophenyl)-5,11-didodecyl-5,11-dihydroindolo[3,2-b]carbazole (4i). Light-yellow crystals, yield
1
10.18 g (50%), mp 148-149 °C. H NMR (500 MHz, C6D6) δ 7.39 – 7.27 (m, 10H), 7.19 (d, J 8.2 Hz, 2H), 7.02 –
6.94 (m, 4H), 3.72 – 3.59 (m, 4H), 1.44 – 1.26 (m, 28H), 1.22 – 1.13 (m, 4H), 1.07 – 0.99 (m, 4H), 0.93 (t, J 6.8
Hz, 6H), 0.87 – 0.78 (m, 4H). 13C NMR (126 MHz, C6D6) δ 143.2, 137.9, 134.5, 133.0, 132.4, 129.4, 126.1, 123.5,
123.2, 122.8, 118.9, 117.3, 108.9, 44.7, 32.3, 30.13, 30.11, 30.03, 30.0, 29.8, 29.6, 29.0, 27.1, 23.1, 14.4. Anal.
Calcd for C54H66Cl2N2: C, 79.68; H, 8.17; N, 3.44 Found: C, 79.69; H, 8.24; N, 3.47.
5,11-Didodecyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole (4j). Light-yellow crystals, yield
1
15.52 g (82%), mp 120-121 °C. H NMR (400 MHz, CDCl3) δ 7.67 (d, J 4.9 Hz, 2H), 7.41 – 7.27 (m, 8H), 7.00 –
6.88 (m, 2H), 6.65 (d, J 8.0 Hz, 2H), 4.10 – 3.73 (m, 4H), 1.70 – 1.58 (m, 4H), 1.36 – 1.17 (m, 32H), 1.14 – 1.01
(m, 4H), 0.88 (t, J 6.7 Hz, 6H). ICZ 4j was previously described in the literature and its analytical data are
identical to the reported data.31
General procedure for C2,8-formylation of ICZ derivatives 4a-j. Dichloromethyl methyl ether (4.1 mL, 45
mmol) was added dropwise to a stirred solution of appropriate ICZ compound 4 (15 mmol) and SnCl4 (5.3 mL,
45 mmol) in dry CH2Cl2 (100 mL) at -20 °C during 15 min. After that, the resulting dark colored solution was
stirred at room temperature for 1 h, and then poured into ice-cold water (200 mL) with conc. HCl (5 mL). The
obtained biphasic mixture was intensively stirred for 30 min and the CH2Cl2 layer was separated, washed with
water (50 mL), 5% KOH aqueous solution (2×25 mL) and dried with anhydrous CaCl2. The solvent was removed
under reduced pressure and the residue was crystallized from DMF (50 mL). The analytically pure product 5
was filtered, washed with EtOH (3×15 mL) and then dried at 120 °C.
5,11-Dihexyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5a). Yellow crystals,
yield 8.64 g (91%), mp 280-281 °C. 1H NMR (500 MHz, CDCl3) δ 9.59 (s, 2H), 7.93 (dd, J 8.6, 1.4 Hz, 2H), 7.76 –
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7.66 (m, 10H), 7.35 (d, J 8.6 Hz, 2H), 6.86 (d, J 1.4 Hz, 2H), 3.94 – 3.86 (m, 4H), 1.60 – 1.52 (m, 4H), 1.28 – 1.19
(m, 4H), 1.12 (dt, J 9.2, 7.1 Hz, 4H), 0.96 – 0.88 (m, 4H), 0.86 (t, J 7.3 Hz, 6H). Dialdehyde 5a was previously
described in the literature and its analytical data are identical to the reported data.33
5,11-Dihexyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde
(5b).
Yellow crystals, yield 9.56 g (92%), mp 257-258 °C. 1H NMR (400 MHz, CDCl3) δ 9.64 (s, 2H), 7.95 (dd, J 8.6, 1.3
Hz, 2H), 7.57 (d, J 8.6 Hz, 4H), 7.35 (d, J 8.6 Hz, 2H), 7.24 (d, J 8.6 Hz, 4H), 6.98 (d, J 1.3 Hz, 2H), 4.02 (s, 6H),
3.98 – 3.90 (m, 4H), 1.62 – 1.52 (m, 4H), 1.28 – 1.19 (m, 4H), 1.18 – 1.08 (m, 4H), 1.03 – 0.92 (m, 4H), 0.87 (t, J
7.2 Hz, 6H). Dialdehyde 5a was previously described in the literature and its analytical data are identical to the
reported data.27
5,11-Dihexyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5c).
Yellow crystals, yield 6.71 g (55%), mp 266-267 °C. 1H NMR (500 MHz, CDCl3) δ 9.71 (s, 2H), 7.99 (dd, J 8.6, 1.2
Hz, 2H), 7.41 (d, J 8.6 Hz, 2H), 7.10 (s, 2H), 6.90 (s, 4H), 4.10 (s, 6H), 4.05 – 3.98 (m, 4H), 3.87 (s, 12H), 1.71 –
1.62 (m, 4H), 1.29 – 1.22 (m, 4H), 1.21 – 1.14 (m, 4H), 1.11 – 1.02 (m, 4H), 0.86 (t, J 7.2 Hz, 6H). 13C NMR (126
MHz, CDCl3) δ 191.2, 154.2, 145.8, 138.8, 132.9, 132.6, 128.1, 127.7, 126.0, 123.1, 122.5, 118.9, 109.0, 107.0,
61.5, 56.3, 44.8, 31.5, 29.5, 26.5, 22.5, 13.9. HRMS (+ESI): Calcd. for C50H57N2O8 m/z 813.4109 [M+H]+, found
m/z 813.4107 [M+H]+.
6,12-Bis(4-chlorophenyl)-5,11-dihexyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5d). Yellow
crystals, yield 9.37 g (89%), mp 300-301 °C. 1H NMR (400 MHz, CDCl3) δ 9.66 (s, 2H), 7.97 (d, J 8.6 Hz, 2H), 7.72
(d, J 8.2 Hz, 4H), 7.63 (d, J 8.4 Hz, 4H), 7.37 (d, J 8.4 Hz, 2H), 6.95 (s, 2H), 3.99 – 3.77 (m, 4H), 1.59 – 1.50 (m,
4H), 1.29 – 1.21 (m, 4H), 1.18 – 1.10 (m, 4H), 1.03 – 0.94 (m, 4H), 0.89 (t, J 7.2 Hz, 6H). 13C NMR (126 MHz,
CDCl3) δ 191.4, 146, 135.9, 135.2, 133.2, 131.6, 129.7, 128.1, 127.6, 126.0, 123.1, 122.4, 117.9, 109.1, 44.9,
31.4, 28.9, 26.4, 22.5, 14.0. Anal. Calcd for C44H42Cl2N2O2: C, 75.31; H, 6.03; N, 3.99; Found: C,75.14; H,5.98;
N,4.16.
5,11-Dihexyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5e). Yellow
crystals, yield 7.35 g (76%), mp 242-243 °C. 1H NMR (400 MHz, CDCl3) δ 9.74 (s, 2H), 7.99 (dd, J 8.6, 1.4 Hz, 2H),
7.79 (dd, J 5.2, 0.9 Hz, 2H), 7.45 (dd, J 5.2, 3.5 Hz, 2H), 7.41 (d, J 8.6 Hz, 2H), 7.38 (d, J 2.7 Hz, 2H), 7.03 – 6.97
(m, 2H), 4.30 – 3.86 (m, 4H), 1.75 – 1.63 (m, 4H), 1.33 – 1.17 (m, 8H), 1.15 – 1.05 (m, 4H), 0.89 (t, J 7.0 Hz, 6H).
Dialdehyde 5e was previously described in the literature and its analytical data are identical to the reported
data.27
5,11-Didodecyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5f). Yellow crystals,
yield 10.11 g (84%), mp 176-177 °C. 1H NMR (400 MHz, CDCl3) δ 9.59 (s, 2H), 7.93 (dd, J 8.6, 1.5 Hz, 2H), 7.77 –
7.65 (m, 10H), 7.35 (d, J 8.6 Hz, 2H), 6.85 (d, J 1.5 Hz, 2H), 3.99 – 3.83 (m, 4H), 1.63 – 1.51 (m, 4H), 1.36 – 1.07
(m, 32H), 0.96 – 0.85 (m, 10H). 13C NMR (126 MHz, CDCl3) δ 191.5, 145.9, 137.6, 133.1, 130.1, 129.4, 128.8,
128.6, 127.9, 125.7, 123.2, 122.7, 119.0, 108.8, 44.8, 31.9, 29.6, 29.59, 29.48, 29.46, 29.3, 29.1, 28.9, 26.6,
22.7, 14.1. Anal. Calcd for C56H68N2O2: C, 83.95; H, 8.56; N, 3.50; Found: C, 83.93; H, 8.75; N, 3.47.
5,11-Didodecyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde
(5g).
Yellow crystals, yield 9.31 g (72%), mp 180-181 °C. 1H NMR (400 MHz, CDCl3) δ 9.64 (s, 2H), 7.94 (dd, J 8.6, 1.5
Hz, 2H), 7.57 (d, J 8.6 Hz, 4H), 7.35 (d, J 8.6 Hz, 2H), 7.23 (d, J 8.6 Hz, 4H), 6.98 (d, J 1.5 Hz, 2H), 4.02 (s, 6H),
3.98 – 3.89 (m, 4H), 1.60 – 1.51 (m, 4H), 1.33 – 1.10 (m, 32H), 1.01 – 0.92 (m, 4H), 0.88 (t, J 6.8 Hz, 6H). 13C
NMR (126 MHz, CDCl3) δ 191.5, 160.2, 145.9, 133.5, 131.2, 129.4, 128.1, 127.8, 125.5, 123.6, 122.8, 118.7,
114.8, 108.8, 55.6, 44.7, 31.9, 29.62, 29.59, 29.54, 29.51, 29.3, 29.2, 29.0, 26.7, 22.7, 14.1. Anal. Calcd for
C58H72N2O4: C, 80.89; H, 8.43; N, 3.25; Found: C, 80.96; H, 8.43; N, 2.96.
5,11-Didodecyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde
1
(5h). Yellow crystals, yield 7.51 g (51%), mp 182-183 °C. H NMR (400 MHz, CDCl3) δ 9.71 (s, 2H), 7.99 (dd, J
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8.6, 1.4 Hz, 2H), 7.41 (d, J 8.6 Hz, 2H), 7.10 (d, J 1.4 Hz, 2H), 6.90 (s, 4H), 4.10 (s, 6H), 4.04 – 3.97 (m, 4H), 3.87
(s, 12H), 1.71 – 1.61 (m, 4H), 1.32 – 1.16 (m, 32H), 1.10 – 1.00 (m, 4H), 0.88 (t, J 6.8 Hz, 6H). 13C NMR (126
MHz, CDCl3) δ 191.3, 154.3, 145.9, 138.9, 133.0, 132.6, 128.1, 127.8, 126, 123.1, 122.5, 119.0, 109.0, 107.0,
61.5, 56.4, 44.8, 31.9, 29.7, 29.6, 29.53, 29.45, 29.34, 29.27, 26.9, 22.6, 14.1 (1 signal (2CAlkyl) was not found
due to overlapping peaks). Anal. Calcd for C62H80N2O8: C, 75.89; H, 8.22; N, 2.85; Found: C, 76.00; H, 8.24; N,
3.08.
6,12-Bis(4-chlorophenyl)-5,11-didodecyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5i). Yellow
1
crystals, yield 10.57 g (81%), mp 237-238 °C. H NMR (400 MHz, CDCl3) δ 9.66 (s, 2H), 7.97 (dd, J 8.6, 1.4 Hz,
2H), 7.72 (d, J 8.3 Hz, 4H), 7.63 (d, J 8.3 Hz, 4H), 7.37 (d, J 8.6 Hz, 2H), 6.95 (d, J 1.3 Hz, 2H), 3.96 – 3.80 (m, 4H),
1.63 – 1.48 (m, 4H), 1.31 – 1.12 (m, 32H), 1.02 – 0.92 (m, 4H), 0.88 (t, J 6.8 Hz, 6H). 13C NMR (126 MHz, CDCl3)
δ 191.3, 145.9, 135.9, 135.2, 133.1, 131.6, 129.7, 128.1, 127.5, 126.0, 123.1, 122.4, 117. 9, 109.1, 44.9, 31.9,
29.6, 29.6, 29.51, 29.49, 29.3, 29.2, 29.0, 26.7, 22.7, 14.1. Anal. Calcd for C56H66Cl2N2O2: C, 77.31; H, 7.65; N,
3.22; Found: C, 77.39; H, 7.52; N, 3.48.
5,11-Didodecyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbaldehyde (5j). Yellow
1
crystals, yield 10.73 g (88%), mp 160-161 °C. H NMR (400 MHz, CDCl3) δ 9.76 (s, 2H), 8.01 (dd, J 8.6, 1.5 Hz,
2H), 7.81 (dd, J 5.2, 1.0 Hz, 2H), 7.47 (dd, J 5.2, 3.4 Hz, 2H), 7.43 (d, J 8.6 Hz, 2H), 7.41 – 7.38 (m, 2H), 7.03 (s,
2H), 4.22 – 3.94 (m, 4H), 1.76 – 1.66 (m, 4H), 1.35 – 1.23 (m, 32H), 1.18 – 1.06 (m, 4H), 0.90 (t, J 6.8 Hz, 6H).
13C NMR (126 MHz, CDCl3) δ 191.5, 145.9, 137.4, 134.4, 128.5, 128.3, 128.1, 127.9, 127.7, 126.3, 124.7, 122.2,
111.8, 109.1, 44.8, 31.9, 29.6, 29.50, 29.48, 29.4, 29.3, 29.3, 29.2, 26.8, 22.7, 14.1. Anal. Calcd for
C52H64N2O2S2: C, 76.80; H, 7.93; N, 3.44; Found: C, 76.75; H, 7.78; N, 3.48.
Procedure for C2-formylation of ICZ 4b. Derivative 4b (1 g, 1.57 mmol) and SnCl4 (0.55 mL, 4.7 mmol) were
dissolved and stirred in dry CH2Cl2 (50 mL). Dichloromethyl methyl ether (180 mg, 1.57 mmol) in dry CH2Cl2 (20
mL) was dropped to the reaction mixture at -20 °C during 15 min and the resulting solution was stirred at
room temperature for 1 h. The reaction mixture was treated with water (40 mL) and conc. HCl (1 mL), organic
layer was separated, washed with water (20 mL), 5% KOH aqueous solution (15 mL) and dried with anhydrous
CaCl2. The CH2Cl2 extract was evaporated under reduced pressure to give desired product 6 in the mixture
with unreacted compound 4b and dialdehyde 5b. This mixture was separated using column chromatography
on silica by eluting with benzene to isolate starting material 4b and next with CH2Cl2 for separation of
monoaldehyde 6 and dialdehyde 5b. It has been obtained ICZ 4b (345 mg, 0.54 mmol), monoaldehyde 6 (205
mg, 0.31 mmol, yield 30% based on the reacted 4b) and dialdehyde 5b (226 mg, 0.33 mmol, yield 32% based
on the reacted 4b).
5,11-Dihexyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2-carbaldehyde (6). Yellow
1
crystals, yield 205 mg (30%), mp 158-159 °C. H NMR (500 MHz, C6D6) δ 9.94 (s, 1H), 8.08 (dd, J 8.5, 1.2 Hz,
1H), 7.51 – 7.47 (m, 5H), 7.38 – 7.34 (m, 1H), 7.22 (d, J 8.2 Hz, 1H), 7.05 (d, J 8.5 Hz, 1H), 7.04 – 6.94 (m, 6H),
3.89 – 3.82 (m, 2H), 3.74 – 3.68 (m, 2H), 3.47 (s, 3H), 3.41 (s, 3H), 1.51 – 1.44 (m, 2H), 1.43 – 1.35 (m, 2H), 1.18
– 1.08 (m, 4H), 1.01 – 0.95 (m, 4H), 0.89 – 0.78 (m, 10H). 13C NMR (126 MHz, C6D6) δ 190.4, 160.5, 160.2,
146.3, 143.3, 134,0, 133.6, 131.9, 131.7, 130.8, 130.7, 128.9, 127.5, 126.22, 126.16, 124.6, 123.91, 123.88,
123.7, 123.2, 119.0, 118.9, 118.8, 115.1, 114.7, 109.04, 108.96, 55.2, 54.9, 44.9, 44.7, 31.71, 31.69, 29.1, 29.0,
26.8, 26.7, 22.9, 14.2 (2 signal (4CAlkyl) were not found due to overlapping peaks). Anal. Calcd for C45H48N2O3: C,
81.29; H, 7.28; N, 4.21; Found: C, 81.34; H, 7.38; N, 4.01.
General procedure for synthesis of 2,8-dicyano-substituted ICZ derivatives (7a-j). An appropriate dialdehyde
5 (1 mmol) was added to a solution of hydroxylamine hydrochloride (280 mg, 4 mmol) and Et3N (0.7 mL, 5
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mmol) in dry DMF (15 mL) and the obtained mixture was stirred and heated at 100 °C for 1 h. After that time,
acetic anhydride (0.95 mL, 10 mmol) was added to this solution and the reaction mixture was stirred and
heated to reflux for another 1 h. The resulting solution was cooled and diluted with EtOH (15 mL) and the
formed precipitate was collected by filtration. Crude material was crystallized from DMF (5 mL) to give
analytically pure product 7, that was filtered, washed with EtOH (2×5 mL) and dried at 120 °C.
5,11-Dihexyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7a). Bright-yellow crystals,
yield 445 mg (71%), mp 324-325 °C. 1H NMR (500 MHz, C6D6) δ 7.39 – 7.35 (m, 4H), 7.32 (dd, J 8.5, 1.5 Hz, 2H),
7.25 – 7.20 (m, 6H), 6.98 (d, J 1.5 Hz, 2H), 6.75 (d, J 8.5 Hz, 2H), 3.59 – 3.47 (m, 4H), 1.30 – 1.21 (m, 4H), 1.15 –
1.07 (m, 4H), 0.97 – 0.88 (m, 4H), 0.82 (t, J 7.3 Hz, 6H), 0.71 – 0.63 (m, 4H). 13C NMR (126 MHz, CDCl3) δ 144.1,
137.1, 133.0, 129.9, 129.6, 129.2, 129.0, 127.4, 122.8, 122.6, 120.7, 119.0, 109.0, 100.7, 44.7, 31.3, 28.8, 26.2,
22.5, 13.9. Anal. Calcd for C44H42N4: C, 84.31; H, 6.75; N, 8.94; Found: C, 84.31; H, 6.98; N, 9.05.
5,11-Dihexyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7b). Bright-
1
yellow crystals, yield 500 mg (73%), mp 293-294 °C. H NMR (400 MHz, CDCl3) δ 7.61 (dd, J 8.5, 1.3 Hz, 1H),
7.53 (d, J 8.6 Hz, 4H), 7.33 (d, J 8.6 Hz, 2H), 7.23 (d, J 8.6 Hz, 4H), 6.93 (d, J 1.3 Hz, 2H), 4.03 (s, 6H), 3.94 – 3.82
(m, 4H), 1.59 – 1.47 (m, 4H), 1.32 – 1.21 (m, 4H), 1.20 – 1.11 (m, 4H), 1.05 – 0.93 (m, 4H), 0.89 (t, J 7.2 Hz, 6H).
1H NMR (400 MHz, C6D6) δ 7.37 – 7.34 (m, 2H), 7.32 (d, J 8.5 Hz, 4H), 7.10 (s, 2H), 6.90 (d, J 8.5 Hz, 4H), 6.79 (d,
J 8.6 Hz, 2H), 3.68 – 3.57 (m, 4H), 3.39 (s, 6H), 1.36 – 1.25 (m, 4H), 1.16 – 1.07 (m, 4H), 0.98 – 0.89 (m, 4H),
0.83 (t, J 7.3 Hz, 6H), 0.79 – 0.69 (m, 4H). 13C NMR (126 MHz, CDCl3) δ 160.2, 144.1, 133.4, 130.9, 128.9,
128.84, 128.77, 127.3, 122.9, 120.8, 118.7, 114.9, 108.9, 100.6, 55.5, 44.6, 31.3, 28.8, 26.3, 22.5, 13.9. Anal.
Calcd for C45H48N2O3: C, 81.29; H, 7.28; N, 4.21; Found: C, 81.34; H, 7.38; N, 4.01.
5,11-Dihexyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile
(7c).
Bright-yellow crystals, yield 484 mg (60%), mp 276-277 °C. 1H NMR (400 MHz, C6D6) δ 7.38 – 7.33 (m, 4H), 6.85
(d, J 9.0 Hz, 2H), 6.79 (s, 4H), 4.15 (s, 6H), 3.84 – 3.73 (m, 4H), 3.35 (s, 12H), 1.45 – 1.34 (m, 4H), 1.18 – 1.08 (m,
4H), 1.02 – 0.93 (m, 4H), 0.89 – 0.77 (m, 10H). 13C NMR (126 MHz, CDCl3) δ 154.3, 144.0, 139.0, 132.9, 132.1,
129.1, 127.4, 122.6, 122.5, 120.5, 118.9, 109.2, 106.7, 101.1, 61.6, 56.3, 44.7, 31.5, 29.4, 26.5, 22.5, 13.9. Anal.
Calcd for C50H54N4O6: C, 74.42; H, 6.74; N, 6.94; Found: C, 74.19; H, 6.69; N, 6.98.
6,12-Bis(4-chlorophenyl)-5,11-dihexyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7d). Bright-
yellow crystals, yield 577 mg (83%), mp ˃ 360 °C. 1H NMR (400 MHz, C6D6) δ 7.34 (dd, J 8.7, 1.1 Hz, 2H), 7.23 –
7.18 (m, 4H), 7.12 – 7.06 (m, 6H), 6.74 (d, J 8.7 Hz, 2H), 3.48 – 3.37 (m, 4H), 1.23 – 1.07 (m, 8H), 0.95 – 0.82 (m,
10H), 0.72 – 0.62 (m, 4H). 13C NMR (126 MHz, CDCl3) δ 144.18, 135.46, 135.33, 133.14, 131.30, 129.84, 129.30,
127.05, 122.49, 122.39, 120.50, 117.89, 109.24, 101.09, 44.78, 31.33, 28.78, 26.32, 22.50, 13.93. 13C NMR (126
MHz, CDCl3) δ 144.1, 136.9, 134.3, 129.3, 128.5, 128.3, 128.2, 127.5, 124.1, 122.3, 120.7, 111.8, 109.3, 101.4,
44.7, 31.3, 29.2, 26.4, 22.5, 13.9. Anal. Calcd for C44H40Cl2N4: C, 75.96; H, 5.80; N, 8.05; Found: C, 75.69; H,
5.60; N, 8.02.
5,11-Dihexyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7e). Bright-yellow
crystals, yield 447 mg (70%), mp 281-282 °C. 1H NMR (400 MHz, CDCl3) δ 7.76 (dd, J 5.2, 1.1 Hz, 2H), 7.64 (dd, J
8.6, 1.3 Hz, 2H), 7.42 (dd, J 5.2, 3.4 Hz, 2H), 7.36 (d, J 8.6 Hz, 2H), 7.34 – 7.30 (m, 2H), 6.84 (d, J 1.3 Hz, 2H),
4.10 – 3.84 (m, 4H), 1.72 – 1.57 (m, 4H), 1.33 – 1.15 (m, 8H), 1.13 – 1.01 (m, 4H), 0.88 (t, J 7.1 Hz, 6H). 13C NMR
(126 MHz, CDCl3) δ 144.1, 136.9, 134.3, 129.3, 128.5, 128.3, 128.2, 127.5, 124.1, 122.3, 120.7, 111.8, 109.3,
101.4, 44.7, 31.3, 29.2, 26.4, 22.5, 13.9. HRMS (+ESI): Calcd. for C40H39N4S2 m/z 639.2611 [M+H]+, found m/z
639.2606 [M+H]+.
5,11-Didodecyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile
(7f).
Bright-yellow
crystals, yield 636 mg (80%), mp 271-272 °C. 1H NMR (400 MHz, C6D6) δ 7.43 – 7.36 (m, 4H), 7.33 (dd, J 8.6, 1.3
Hz, 2H), 7.28 – 7.20 (m, 6H), 6.99 (d, J 1.3 Hz, 2H), 6.78 (d, J 8.6 Hz, 2H), 3.63 – 3.46 (m, 4H), 1.37 – 1.21 (m,
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28H), 1.20 – 1.11 (m, 4H), 1.05 – 0.96 (m, 4H), 0.93 (t, J 6.7 Hz, 6H), 0.78 – 0.68 (m, 4H). 13C NMR (126 MHz,
C6D6) δ 144.4, 137.6, 133.3, 130.1, 129.7, 129.2, 129.1, 123.4, 123.3, 120.5, 119.6, 109.4, 102.2, 44.7, 32.3,
30.07, 30.05, 29.94, 29.88, 29.8, 29.5, 29.0, 26.8, 23.1, 14.3 (1 signal (2CAryl) was not found due to overlapping
peaks). Anal. Calcd for C56H66N4: C, 84.59; H, 8.37; N, 7.05 Found: C, 84.53; H, 8.38; N, 7.10.
5,11-Didodecyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile
(7g).
Bright-yellow crystals, yield 684 mg (80%), mp 218-219 °C. 1H NMR (400 MHz, C6D6) δ 7.37 – 7.31 (m, 6H), 7.22
(d, J 1.3 Hz, 2H), 6.93 (d, J 8.5 Hz, 4H), 6.82 (d, J 8.6 Hz, 2H), 3.72 – 3.62 (m, 4H), 3.42 (s, 6H), 1.40 – 1.22 (m,
28H), 1.20 – 1.12 (m, 4H), 1.07 – 0.97 (m, 4H), 0.93 (t, J 6.7 Hz, 6H), 0.85 – 0.76 (m, 4H). 13C NMR (126 MHz,
C6D6) δ 160.8, 144.4, 133.9, 131.3, 129.3, 129.1, 123.8, 123.6, 120.6, 119.4, 115.3, 109.4, 102.1, 55.3, 44.8,
32.3, 30.11, 30.09, 30.01, 29.97, 29.8, 29.6, 29.1, 27.0, 23.1, 14.4 (1 signal (2CAryl) was not found due to
overlapping peaks). Anal. Calcd for C58H70N4O2: C, 81.46; H, 8.25; N, 6.55; Found: C, 81.20; H, 8.36; N, 6.39.
5,11-Didodecyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7h).
Bright-yellow crystals, yield 810 mg (83%), mp 191-192 °C. 1H NMR (500 MHz, C6D6) δ 7.40 – 7.33 (m, 2H), 6.86
(d, J 8.9 Hz, 2H), 6.81 (s, 4H), 4.16 (s, 6H), 3.86 – 3.77 (m, 4H), 3.37 (s, 12H), 1.49 – 1.41 (m, 4H), 1.37 – 1.23 (m,
24H), 1.21 – 1.13 (m, 4H), 1.10 – 1.00 (m, 4H), 0.95 – 0.84 (m, 10H). 13C NMR (126 MHz, C6D6) δ 155.4, 144.4,
140.7, 133.5, 132.4, 129.2, 123.5, 123.3, 120.4, 119.8, 109.7, 107.7, 102.5, 61.5, 56.2, 44.9, 32.3, 30.2, 30.04,
29.98, 29.92, 29.88, 29.8, 29.7, 27.1, 23.1, 14.3 (1 signal (2CAryl) was not found due to overlapping peaks).
HRMS (+ESI): Calcd. for C62H82N5O6 m/z 992.6260 [M+NH4]+, found m/z 992.6255 [M+NH4]+.
6,12-Bis(4-chlorophenyl)-5,11-didodecyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7i). Bright-
yellow crystals, yield 743 mg (86%), mp 310-311 °C. 1H NMR (500 MHz, C6D6) δ 7.34 (dd, J 8.5, 1.0 Hz, 2H), 7.20
(d, J 8.2 Hz, 4H), 7.12 (d, J 8.2 Hz, 4H), 7.08 (s, 2H), 6.77 (d, J 8.5 Hz, 2H), 3.56 – 3.36 (m, 4H), 1.39 – 1.14 (m,
32H), 1.03 – 0.96 (m, 4H), 0.94 (t, J 6.8 Hz, 6H), 0.77 – 0.69 (m, 4H). 13C NMR (126 MHz, C6D6) δ 144.3, 135.6,
133.4, 131.6, 130.0, 129.4, 127.5, 127.4, 123.0, 120.2, 118.4, 109.6, 102.6, 44.7, 32.3, 30.09, 30.08, 29.9, 29.8,
29.5, 29.0, 26.9, 23.1, 14.3 (2 signal (2CAryl and 2CAlkyl) were not found due to overlapping peaks). Anal. Calcd
for C56H64Cl2N4: C, 77.84; H, 7.47; N, 6.48; Found: C, 77.95; H, 7.34; N, 6.43.
5,11-Didodecyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-dicarbonitrile (7j). Bright-
yellow crystals, yield 565 mg (70%), mp 192-193 °C. 1H NMR (500 MHz, C6D6) δ 7.35 (dd, J 8.5, 1.5 Hz, 2H), 7.11
– 7.04 (m, 4H), 6.99 – 6.94 (m, 2H), 6.91 – 6.86 (m, 2H), 6.77 (d, J 8.5 Hz, 2H), 3.68 (t, J 8.3 Hz, 4H), 1.47 – 1.24
(m, 28H), 1.24 – 1.16 (m, 4H), 1.14 – 1.05 (m, 4H), 0.97 – 0.84 (m, 10H). 13C NMR (126 MHz, C6D6) δ 144.2,
137.4, 134.5, 129.4, 128.7, 128.3, 127.7, 124.8, 122.8, 120.5, 112.2, 109.7, 102.7, 44.7, 32.3, 30.1, 30.0, 29.9,
29.8, 29.6, 29.5, 29.4, 27.0, 23.1, 14.3 (1 signal (2CAryl) was not found due to overlapping peaks). HRMS (+ESI):
Calcd. for C52H63N4S2 m/z 807.4489 [M+H]+, found m/z 807.4498 [M+H]+.
General procedure for synthesis of 2,8-bis(benzo[d]thiazol-2-yl)-substituted ICZ derivatives (8f-j). 2-
Aminothiophenol (0.32 mL, 3 mmol) was added to a suspension of dialdehyde 5 (1 mmol) in DMSO (15 mL)
and the resulting mixture was stirred and heated at 160 °C for 1 h. After that time, it cooled to room
temperature and the formed precipitate was filtered and washed with EtOH (10 mL). Crude matter was
purified by crystallization form DMF (15 mL), filtered, washed with EtOH (10 mL) and dried at 120 °C to give
analytically pure form of product 8.
2,2'-(5,11-Didodecyl-6,12-diphenyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-diyl)bis(benzo[d]thiazole) (8f).
1
Orange crystals, yield 840 mg (83%), mp 196-197 °C. H NMR (400 MHz, C6D6) δ 8.76 (dd, J 8.6, 1.5 Hz, 2H),
8.16 (d, J 8.0 Hz, 2H), 7.67 – 7.59 (m, 6H), 7.58 – 7.48 (m, 8H), 7.24 – 7.17 (m, 4H), 7.01 (t, J 7.5 Hz, 2H), 3.81 –
3.67 (m, 4H), 1.53 – 1.41 (m, 4H), 1.37 – 1.16 (m, 28H), 1.12 – 1.02 (m, 4H), 0.92 (t, J 6.7 Hz, 6H), 0.88 – 0.79
(m, 4H). 13C NMR (126 MHz, CDCl3) δ 169.6, 154.1, 144.1, 138.0, 134.8, 132.8, 130.2, 129.4, 128.9, 125.9,
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124.7, 124.3, 123.8, 123.2, 123.0, 122.96, 122.4, 121.3, 118.7, 108.7, 44.6, 31.9, 29.6, 29.58, 29.54, 29.52,
29.4, 29.2, 28.9, 26.6, 22.7, 14.1. Anal. Calcd for C68H74N4S2: C, 80.75; H, 7.37; N, 5.54; Found: C, 80.85; H, 7.51;
N, 5.72.
2,2'-(5,11-Didodecyl-6,12-bis(4-methoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-diyl)bis(benzo[d]-
1
thiazole) (8g). Orange crystals, yield 900 mg (84%), mp 228-229 °C. H NMR (400 MHz, CDCl3) δ 8.34 (d, J 8.2
Hz, 2H), 8.03 (d, J 8.2 Hz, 2H), 7.85 (d, J 7.7 Hz, 2H), 7.62 (d, J 8.6 Hz, 4H), 7.50 – 7.42 (m, 2H), 7.41 – 7.32 (m,
4H), 7.29 (d, J 8.6 Hz, 4H), 7.00 (d, J 1.5 Hz, 2H), 4.09 (s, 6H), 4.07 – 3.93 (m, 4H), 1.66 – 1.55 (m, 4H), 1.35 –
1.09 (m, 32H), 1.06 – 0.95 (m, 4H), 0.88 (t, J 6.8 Hz, 6H). 13C NMR (126 MHz, CDCl3) δ 169.8, 160.0, 154.1,
144.0, 134.7, 133.1, 131.3, 129.9, 126.0, 124.5, 124.3, 123.6, 123.3, 123.2, 123.1, 122.4, 121.2, 118.3, 114.9,
108.6, 55.5, 44.6, 31.9, 29.7, 29.64, 29.61, 29.58, 29.4, 29.2, 29.0, 26.8, 22.7, 14.1. Anal. Calcd for
C70H78N4O2S2: C, 78.46; H, 7.34; N, 5.23; Found: C, 78.59; H, 7.28; N, 5.54.
2,2'-(5,11-Didodecyl-6,12-bis(3,4,5-trimethoxyphenyl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-diyl)bis-
(benzo[d]thiazole) (8h). Orange crystals, yield 950 mg (80%), mp 205-206 °C. 1H NMR (400 MHz, CDCl3) δ 8.42
(d, J 8.3 Hz, 2H), 8.05 (d, J 8.3 Hz, 2H), 7.83 (d, J 7.6 Hz, 2H), 7.53 – 7.37 (m, 6H), 7.37 – 7.32 (m, 1H), 6.98 (s,
4H), 4.19 (s, 6H), 4.06 – 3.95 (m, 4H), 3.90 (s, 12H), 1.73 – 1.61 (m, 4H), 1.34 – 1.15 (m, 32H), 1.12 – 1.00 (m,
4H), 0.87 (t, J 6.8 Hz, 6H). 13C NMR (126 MHz, CDCl3) δ 169.6, 154.3, 144.2, 138.5, 134.5, 132.98, 132.95, 126.2,
125.0, 124.6, 123.8, 123.5, 123.3, 122.9, 122.8, 122.4, 121.5, 118.7, 109.0, 107.1, 61.2, 56.4, 44.8, 31.9, 29.62,
29.59, 29.5, 29.3, 27.0, 22.7, 14.1. Anal. Calcd for C74H86N4O6S2: C, 74.59; H, 7.27; N, 4.70; Found: C, 74.66; H,
7.45; N, 4.63.
2,2'-(6,12-Bis(4-chlorophenyl)-5,11-didodecyl-5,11-dihydroindolo[3,2-b]carbazole-2,8-diyl)bis(benzo[d]-
1
thiazole) (8i). Orange crystals, yield 1 g (93%), mp 237-238 °C. H NMR (400 MHz, CDCl3) δ 8.33 (d, J 8.3 Hz,
2H), 8.05 (d, J 7.9 Hz, 1H), 7.89 (d, J 7.9 Hz, 1H), 7.77 (d, J 8.3 Hz, 4H), 7.68 (d, J 8.3 Hz, 4H), 7.50 – 7.44 (m, 2H),
7.41 – 7.30 (m, 4H), 6.97 (d, J 1.6 Hz, 2H), 4.10 – 3.88 (m, 4H), 1.67 – 1.53 (m, 4H), 1.30 – 1.11 (m, 32H), 1.06 –
0.94 (m, 4H), 0.88 (t, J 6.8 Hz, 6H). 1H NMR (400 MHz, C6D6) δ 8.68 (dd, J 8.6, 1.6 Hz, 2H), 8.26 (d, J 8.0 Hz, 2H),
7.63 (d, J 7.5 Hz, 2H), 7.49 (d, J 8.3 Hz, 4H), 7.44 (d, J 1.6 Hz, 2H), 7.36 (d, J 8.3 Hz, 4H), 7.24 – 7.19 (m, 2H), 7.14
– 7.12 (m, 2H), 7.06 – 7.00 (m, 2H), 3.83 – 3.66 (m, 4H), 1.49 – 1.39 (m, 4H), 1.38 – 1.28 (m, 24H), 1.25 – 1.18
(m, 4H), 1.09 – 1.00 (m, 4H), 0.96 – 0.90 (m, 6H), 0.89 – 0.81 (m, 4H). 13C NMR (126 MHz, CDCl3) δ 169.5,
153.8, 144.1, 136.5, 135.2, 134.6, 132.8, 131.7, 129.8, 126.2, 124.9, 124.6, 123.8, 123.1, 122.9, 122.7, 122.5,
121.4, 117.5, 108.9, 44.7, 31.9, 29.7, 29.64, 29.56, 29.4, 29.2, 29.1, 29.0, 26.8, 22.7, 14.1. Anal. Calcd for
C68H72Cl2N4S2: C, 75.60; H, 6.72; N, 5.19; Found: C, 75.65; H, 6.72; N, 5.32.
2,2'-(5,11-Didodecyl-6,12-di(thiophen-2-yl)-5,11-dihydroindolo[3,2-b]carbazole-2,8-diyl)bis(benzo[d]-
1
thiazole) (8j). Orange crystals, yield 930 mg (91%), mp 225-226 °C. H NMR (400 MHz, C6D6) δ 8.81 (dd, J 8.7,
1.6 Hz, 2H), 8.20 (d, J 7.8 Hz, 2H), 7.70 – 7.57 (m, 4H), 7.42 (d, J 4.4 Hz, 2H), 7.27 – 7.18 (m, 8H), 7.07 – 7.01 (m,
2H), 3.96 – 3.76 (m, 4H), 1.65 – 1.49 (m, 4H), 1.39 – 1.20 (m, 28H), 1.19 – 1.10 (m, 4H), 1.05 – 0.95 (m, 4H),
0.92 (t, J 6.7 Hz, 6H). 13C NMR (126 MHz, CDCl3) δ 169.8, 153.2, 144.3, 138.0, 134.3, 128.6, 128.3, 128.2, 128.0,
126.2, 125.4, 124.8, 124.6, 123.8, 123.2, 122.6, 122.4, 121.4, 111.5, 109.2, 44.8, 31.9, 29.7, 29.57, 29.56,
29.39, 29.35, 29.31, 29.26, 26.9, 22.7, 14.1. Anal. Calcd for C64H70N4S4: C, 75.10; H, 6.89; N, 5.47; Found: C,
75.20; H, 6.70; N, 5.66.
Acknowledgements
This research study was supported financially by the Russian Science Foundation (Project No. 16-13-10435).
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