Diaza-analogs of benzopyrene and perylene containing thienyl and 4-(phenylamino)phenyl groups: Synthesis, characterization, optical and electrochemical properties

Article abstract of DOI:10.1016/j.dyepig.2016.09.026

Series of 1,8-diazabenzopyrenes and 1,7-diazaperylenes with thienyl or 4-(phenylamino)phenyl groups were designed and synthesized by a one-pot process from the functionalized terminal alkynes and either 1,4- or 1,5-diiodoanthraquinones in order to investigate the effect of extending π-conjugation at the 2,7- and 2,8-positions on the optical and electrochemical properties. The substances synthesized were characterized by X-ray analysis, cyclic voltammetry, UV–vis and luminescence spectroscopy. Energies and spin-densities of frontier molecular orbitals were calculated by DFT. Practically planar crystal structures of 1,8-diazabenzopyrene and 1,7-diazaperylene with thienyl groups were confirmed by X-ray diffraction data. Solid-state luminescence was obtained for the synthesized substances in drop-casted films and in 1,4-dioxane/water mixtures.

Full text of DOI:10.1016/j.dyepig.2016.09.026

Accepted Manuscript
Diaza-analogs of benzopyrene and perylene containing thienyl and 4-
(Phenylamino)phenyl groups: Synthesis, characterization, optical and electrochemical
properties
Denis S. Baranov, Mikhail N. Uvarov, Maxim S. Kazantsev, Evgeny A. Mostovich,
Evgeni M. Glebov, Yurii V. Gatilov, Leonid V. Kulik
PII:
S0143-7208(16)30716-1
10.1016/j.dyepig.2016.09.026
DYPI 5478
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 30 May 2016
Revised Date: 1 September 2016
Accepted Date: 12 September 2016
Please cite this article as: Baranov DS, Uvarov MN, Kazantsev MS, Mostovich EA, Glebov EM, Gatilov
YV, Kulik LV, Diaza-analogs of benzopyrene and perylene containing thienyl and 4-(Phenylamino)phenyl
groups: Synthesis, characterization, optical and electrochemical properties, Dyes and Pigments (2016),
doi: 10.1016/j.dyepig.2016.09.026.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Diaza-analogs of Benzopyrene and Perylene Containing Thienyl and
-(Phenylamino)phenyl Groups: Synthesis, Characterization,
Optical and Electrochemical Properties
4
.
a,b
a
b,c
b,c
Denis S. Baranov , Mikhail N. Uvarov , Maxim S. Kazantsev , Evgeny A. Mostovich ,
a,b
b,c
a,b
Evgeni M. Glebov , Yurii V. Gatilov, and Leonid V. Kulik
a
V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian
Academy of Science, 630090 Novosibirsk, Russian Federation. Fax: +7(383)3307350;
b
Novosibirsk State University, 630090 Novosibirsk, Russian Federation.
c
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry , Siberian Branch of the Russian
Academy of Science, 630090 Novosibirsk, Russian Federation
ABSTRACT
Series
of
1,8-diazabenzopyrenes
and
1,7-diazaperylenes
with
thienyl
or
4
-(phenylamino)phenyl groups were designed and synthesized by a one-pot process from the
functionalized terminal alkynes and either 1,4- or 1,5-diiodoanthraquinones in order to
investigate the effect of extending π-conjugation at the 2,7- and 2,8-positions on the optical and
electrochemical properties. The substances synthesized were characterized by X-ray analysis,
cyclic voltammetry, UV-vis and luminescence spectroscopy. Energies and spin-densities of
frontier molecular orbitals were calculated by DFT. Practically planar crystal structures of 1,8-
diazabenzopyrene and 1,7-diazaperylene with thienyl groups were confirmed by X-ray
diffraction data. Solid-state luminescence was obtained for the synthesized substances in drop-
casted films and in 1,4-dioxane/water mixtures.
1

ACCEPTED MANUSCRIPT
Keywords:
diazabenzopyrenes, diazaperylenes, push-pull polycondensed small molecules, solid-state
luminescence
1
. Introduction
Organic polycondensed materials such as chemically modified pyrenes and perylenes [1] could
be applied in organic electronics [2, 3], in particular, in planar- and bulk-heterojunction organic
photovoltaic devices as acceptor [4-6] or donor [7] small molecules, as light absorber in dye-
sensitized solar cells [8] and as semiconducting materials in organic field-effect transistors [9-
1
3]. In some cases significant changes of optical properties and fluorescence quantum yield of
such substances arise from even apparent insignificant chemical modifications of the molecules
14-16]. Moreover surrounding media could change color and fluorescence intensity
[
dramatically which allows the application of such substances as chemosensors for metal ions in
solutions [17-20] and as fluorescent indicators of solvent polarity and pH sensors [21-22]. High
values of luminescence yields allow to use such polycondensed molecules in emitting layers of
organic light emitting devices [20, 23-27].
Previously, we have presented a synthetic route to obtain diazaperylenes [28] and
diazabenzopyrenes [29] containing aliphatic substituents. In this synthetic route the main
chemical transformations were based on annulation of the two pyridine rings to the
anthraquinone core by reaction of the bis(R-ethynyl)anthraquinones with urea in DMF. Note that
this synthetic approach is quite simple and does not require organometallic compounds or
aggressive conditions. New aza-analogues of perylene and benzopyrene containing thienyl and
4
-(phenylamino)phenyl groups are promising for organic electronic applications because thienyl
π-conjugated group is the most popular building unit for organic semiconductor materials and
phenylamines are widely used in light-emitting diodes as hole-transporting and emissive layers
[
30].
2

ACCEPTED MANUSCRIPT
In the present paper we report a one-pot synthesis of new aza-analogues of perylene and
benzopyrene containing thienyl and 4-(phenylamino)phenyl groups. The synthesized substances
were characterized by X-ray analysis, cyclic voltammetry, UV-vis and luminescence
spectroscopy to indicate possible applications of these materials.
2
.Experimental
2
.1. General
Elemental analyses were performed with a CHN-analyzer (Model 1106, ‘Carlo Erba’, Italy).
1
13
The H and C NMR spectra were recorded on a Bruker AV-400 spectrometer. Melting points
were determined with a Kofler apparatus. Mass spectra were measured on a Thermo Electron
Corporation DFS mass spectrometer (70 eV), using direct injection, the temperature of the
ionization chamber was 220-270ºC. The IR-spectra were recorded on a Shimadzu IRTracer-100
instrument with GS10802-X Quest ATR ZnSe Accessory (Specac). Cyclic voltammetry (CVA)
measurement were performed in CH Cl solution on a computer controlled P-8nano
2
2
potentiostat/galvanostat (Elins) in combination with three-electrode cell (Gamry), 0.1 M
tetrabutylammonium hexafluorophosphate being used as supporting electrolyte. The Pt-disc, Pt
wire and Ag/AgCl were used as working, counter and reference electrode respectively. The
reference electrode was calibrated by measuring the redox potentials of ferrocene.
The HOMO and LUMO energy levels were estimated using onset oxidation and reduction
+
potentials measured vs Fc/Fc in the cyclic voltammograms according to Eqs. (1) and (2):
onset
Ehomo= -e(Eox
Elumo= -e(Ered
+4.8) (eV)
+4.8) (eV)
(1)
(2)
onset
Column chromatography was performed on alumina (50-150 µm, TU 6-09-3916-75) and the
Kieselgel 60 plates (Merck) were used for TLC analysis. All reagents were purchased from
commercial chemical suppliers.
3

ACCEPTED MANUSCRIPT
For preliminary geometry optimization semi-empirical AM1 from MOPAC 2012 was used
[
31]. Final geometry optimization step was done with ORCA 3.0.1 [32] package by DFT B3LYP
using a balanced polarized triple-zeta basis set def2-TZVP [33-34]. All visualizations were done
by using Gabedit 2.4.8 software [35]. All DFT calculations were performed using Siberian
Supercomputing Center [36].
The UV-Vis absorption spectra were recorded using an Agilent 8453 spectrophotometer
(Agilent Technologies), and luminescence spectra were recorded using FLSP-920
spectrofluorimeter (Edinburgh Instruments) in toluene, 1,4-dioxane (dioxane) or dioxane/water
-5
mixture solutions with the concentrations 10 M. Excitation at 375 nm was used to record
luminescence spectra and kinetics. The solutions in dioxane/water mixtures were prepared by
adding of water into dioxane. Molar absorption coefficients ε were determined at maximum
absorption in the visible spectral region. Photoluminescence quantum yield ϕ values were
determined using the ethanol solution of Coumarine 153 as standard (φC153= 0.38) [37].
The analytical and spectroscopic investigations were carried out at the Multi-Access Chemical
Service Center of the Siberian Branch of the Russian Academy of Sciences. XRD data for
compounds 8b, 9b were obtained on a Bruker Kappa Apex II CCD diffractometer using ϕ, ω
scans of narrow (0.5º) frames with Mo Kα radiation (λ = 0.71073 Å) and a graphite
monochromator at room temperature.
2
.2. Synthesis
N-Octyldiphenylamine (1)
A mixture of diphenylamine (10 g, 0.056 mol), octyl bromide (12 g, 0.062 mol),
benzyltriethylammonium chloride (BTEAC) (1.4 g, 6.0 mmol), NaOH (12 g, 0.3 mol) and H O
2
(10 mL) was vigorously stirred for 24 h at reflux temperature (Scheme 1). After cooling, the
organic layer was separated. The crude product was purified by column chromatography on
1
alumina (elution with petroleum ether). Yield 14.4 g (87%), colorless oil. H NMR (CDCl , 400
3
4

ACCEPTED MANUSCRIPT
MHz) δ: 0.88 (3H, t, J 6.9 Hz, Me), 1.28 (10H, m, (CH ) ), 1.66 (2H, m, CH ), 3.68 (CH, t, J 7.8
2
5
2
1
Hz, NCH ), 6.94 (2H, m, H ), 6.99 (4H, m, H ), 7.26 (4H, m, H ) ppm ( H NMR Ref. [38]).
2
Ar
Ar
Ar
4
-Iodo-N-octyldiphenylamine (2)
Powdered iodine (11.6 g, 0.046 mol) was added portions over 0.5 h to a vigorously stirred
mixture of the diphenylamine 1 (13 g, 0.046 mol), KHCO (7 g, 0.07 mol) and H O (40 mL) at
3
2
room temperature. The reaction mixture at room temperature was stirred for 2 h. After ethyl
acetate (100 mL) was added, the organic layer was washed with solution Na SO , dried over
2
3
MgSO and concentrated on rotary evaporator. The crude product was purified by column
4
1
chromatography on alumina (elution with petroleum ether). Yield 9.8 g (52%), colorless oil. H
NMR (CDCl , 400 MHz) δ: 0.88 (3H, t, J 6.9 Hz, Me), 1.28 (10H, m, (CH ) ), 1.63 (2H, m,
3
2 5
CH ), 3.64 (2H, t, J 7.8 Hz, NCH ), 6.66 (2H, dt, J 3.1, 8.9 Hz, H ), 7.05 (3H, m, H ), 7.30
2
2
Ar
Ar
1
3
(
2H, m, H ), 7.47 (2H, dt, J 3.1, 8.9 Hz, H ) ppm. C NMR (CDCl , 100 MHz) δ: 14.25,
Ar Ar 3
2
2.77, 27.17, 27.40, 29.42, 29.51, 31.93, 52.46 (C H ), 81.46 (CI), 120.79 (2CH), 123.03 (CH),
8 17
1
23.38 (2CH), 129.63 (2CH), 137.95 (2CH), 147.47 (C), 148.05 (C) ppm. HMRS, found:
+
+
[
M+H] m/z 407.1107; C H NI [M+H] 407.1104.
20 26
1
-((4-(Octyl(phenyl)amino)phenyl)ethynyl)cyclopentanol (3)
Under argon, a mixture of the iodide 2 (8.6 g, 0.021 mol), 1-ethynylcyclopentanol (3.3 g, 0.03
mol), PdCl (PPh ) (40 mg, 0.056 mmol), CuI (20 mg, 0.1 mmol), Na CO (3 g, 0.028 mol), H O
2
3 2
2
3
2
о
(
3 mL) and Et NH (8 mL) in 30 mL of toluene was stirred for 3 h at 80 С. After cooling, the
2
organic layer was washed with water (250 mL), dried over MgSO . The crude product was
4
purified by column chromatography on alumina (elution with toluene). Yield 7.5 g (92%), light
-1
1
yellow oil. IR (neat, cm ): 2953, 2924, 2855 (Alk), 2220 (C≡C). H NMR (CDCl , 400 MHz) δ:
3
0
.87 (3H, t, J 6.9 Hz, Me), 1.27 (10H, m, (CH ) ), 1.64 (2H, m, CH ), 1.78 (2H, m, CH ), 1.86
2 5 2 2
(
2H, m, CH ), 2.02 (4H, m, (CH ) ), 3.66 (2H, t, J 7.8 Hz, NCH ), 6.75 (2H, dt, J 2.7, 8.7 Hz,
2 2 2 2
5

ACCEPTED MANUSCRIPT
1
3
H ), 7.09 (3H, m, H ), 7.25 (2H, dt, J 2.7, 8.7 Hz, H ), 7.32 (2H, m, H ) ppm. C NMR
Ar
Ar
Ar
Ar
(
CDCl , 100 MHz) δ: 14.25, 22.77, 23.65 (2C), 27.16, 27.45, 29.41, 29.51, 31.93, 42.74 (2C),
3
5
1
2.44, 75.20 (Alk), 83.71, 91.23 (C≡C), 112.71 (C), 117.10 (2CH), 123.59 (CH), 124.44 (2CH),
29.66 (2CH), 132.70 (2CH), 147.31 (C), 148.22 (C) ppm. Found: C, 82.86; H, 8.72; N, 3.50%;
+
C H NO C, 83.24; H, 9.06; N, 3.60%. HMRS, found: [M+H] m/z 389.2708; C H NO
27
35
27 35
+
[
M+H] 389.2713.
4
-Ethynyl-N-octyldiphenylamine (4)
To a solution of the alkynol 3 (2 g, 5.1 mmol) in dry toluene (10 mL) anhydrous powdered
KOH was added (400 mg, 7.1 mmol), and the mixture was stirred at reflux for 0.5 h. After
cooling, petroleum ether (20 mL) was added and the reaction mixture was flash
chromatographed on alumina (elution with petroleum ether). Yield 1.3 g (83%), light yellow oil.
-1
1
IR (neat, cm ): 3304 (≡CH), 2953, 2922, 2853 (C H ), 2102 (C≡C). H NMR (CDCl , 400
8
17
3
MHz) δ: 0.88 (3H, t, Me, J 6.9 Hz), 1.28 (10H, m, (CH ) ), 1.65 (2H, m, CH ), 2.99 (1H, s,
2
5
2
≡
CH), 3.67 (2H, t, J 7.8 Hz, NCH ), 6.73 (2H, dt, J 2.7, 9.0 Hz, H ), 7.12 (2H, m, H ), 7.33
2 Ar Ar
1
3
(
4H, m, H ) ppm. C NMR (CDCl , 100 MHz) δ: 14.24, 22.77, 27.16, 27.45, 29.41, 29.51,
Ar 3
3
1.93, 52.48 (C H ), 75.41 (≡CH), 84.60 (-C≡), 111.40 (C), 116.37 (2CH), 124.14 (CH), 125.16
8 17
(2CH), 129.76 (2CH), 133.23 (2CH), 147.11 (C), 148.73 (C) ppm. Found: C, 86.36; H, 9.08; N,
4
.42%; C H N C, 86.51; H, 8.91; N, 4.59%.
22
27
Copper (I) thien-2-ylacetylide (5)
A mixture of CuCl (4.2 g, 0.042 mol), NH Cl (8.8 g, 0.1 mol), NH OHꢀHCl (0.9 g, 0.013 mol),
4
2
2
5% aqueous NH (21 mL) in H O (160 mL) was stirred at room temperature under argon
3
2
atmosphere. After stirring for 20 min, 2-ethynylthiophene (3.6 g, 0.033 mol) was added into the
mixture over a period of 1 h. After stirring the reaction mixture for a further 4 h, the yellow
6

ACCEPTED MANUSCRIPT
precipitate copper acetylide was filtered, washed with EtOH, and dried in vacuum. Yield 5.25 g
(94%).
Synthesis of Bis(R-ethynyl)-9,10-anthraquinones (general procedure)
Under argon, a mixture of diiodo-9,10-anthraquinone (500 mg, 1.1 mmol), the alkyne 4 (920
mg, 3.0 mmol), PdCl (PPh ) (20 mg, 0.028 mmol), CuI (10 mg, 0.052 mmol), Et N (2 mL) in
2
3 2
3
о
toluene (15 mL) was stirred for 8-9 h at 75 С. Then the reaction mixture was cooled, solvent
was evaporated on rotary evaporator and was chromatographed on alumina (elution with
petroleum ether). Subsequent recrystallization from mixture of petroleum ether - toluene gave
pure compounds.
1
,4-Bis((4-(Octyl(phenyl)amino)phenyl)ethynyl)-9,10-anthraquinone (6a). Yield 220 mg
-1
1
(
25%), mp 93-95 ºC. IR (neat, cm ): 2949, 2920, 2851 (C H ), 2176 (C≡C), 1672 (C=O). H
8 17
NMR (CDCl , 400 MHz) δ: 0.89 (6H, t, J 6.9 Hz, 2Me), 1.30 (20H, m, 2(CH ) ), 1.69 (4H, m,
3
2 5
2
CH ), 3.72 (4H, t, J 7.8 Hz, 2NCH ), 6.81 (4H, d, J 8.8 Hz, H ), 7.15 (2H, m, H ), 7.18 (4H,
2 2 Ar Ar
d, J 7.8 Hz, H ), 7.37 (4H, d, J 7.8 Hz, H ), 7.56 (4H, d, J 8.8 Hz, H ), 7.77 (2H, m, H ), 7.81
Ar
Ar
Ar
Ar
1
3
(
2H, s, H ), 8.31 (2H, m, H ) ppm. C NMR (CDCl , 100 MHz) δ: 14.26, 22.78, 27.18, 27.49,
Ar Ar 3
2
9.43, 29.53, 31.94, 52.54 (2C H ), 89.34, 99.23 (2C≡C), 112.35 (2C), 116.20 (4CH), 123.58
8 17
(2C), 124.41 (2CH), 125.50 (4CH), 127.16 (2C), 129.79 (4CH), 133.59 (4CH), 133.68 (2CH),
1
33.82 (2CH), 133.94 (2C), 138.39 (2CH), 147.00 (2C), 149.02 (2C), 182.02 (2C=O) pm.
+
+
HMRS, found: [M+H] m/z 814.4472; C H N O [M+H] 814.4493.
58
58
2
2
1
,5-Bis((4-(octyl(phenyl)amino)phenyl)ethynyl)-9,10-anthraquinone (7a). Yield 290 mg
-1
1
(
33%), mp 124-125 ºC. IR (neat, cm ): 2949, 2920, 2849 (C H ), 2183 (C≡C), 1665 (C=O). H
8 17
NMR (CDCl , 400 MHz) δ: 088 (6H, t, J 6.9 Hz, 2Me), 1.29 (20H, m, 2(CH ) ), 1.69 (4H,m,
3
2 5
2
CH ), 3.72 (4H, t, J 7.7 Hz, 2NCH ), 6.82 (4H, dt, J 2.5, 8.9 Hz, H ), 7.15 (6H, m, H ), 7.37
2 2 Ar Ar
(
4H, m, H ), 7.55 (4H, dt, J 2.5, 8.9 Hz, H ), 7.70 (2H, t, J 7.8 Hz, H ), 7.90 (2H, dd, J 1.3,
Ar Ar Ar
7

ACCEPTED MANUSCRIPT
1
3
7
2
1
.8 Hz, H ), 8.31 (2H, dd, J 1.3, 7.8 Hz, H ) ppm. C NMR (CDCl , 100 MHz) δ: 14.27,
Ar Ar 3
2.79, 27.19, 27.48, 29.44, 29.54, 31.95, 52.54 (2C H ), 88.43, 97.63 (2C≡C), 112.40 (2C),
8
17
16.35 (4CH), 124.25 (2CH), 124.29 (2CH), 125.35 (4CH), 127.01 (2C), 129.78 (4CH), 132.20
(2C), 132.99 (2CH), 133.49 (4CH), 135.44 (2C), 139.48 (2CH), 147.06 (2C), 148.92 (2C),
1
81.96 (2C=O) ppm. Found: C, 85.75; H, 6.93; N, 3.39%; C H N O C, 85.47; H, 7.17; N,
58 58 2 2
3
.44%.
Synthesis
of
2,7-DiR-naphtho[4,3,2,1-lmn][2,9]phenanthroline
and
2,8-DiR-
benzo[de]isoquino[1,8-gh]quinoline (general procedure).
Method A
A mixture of bis(R-ethynyl)-9,10-anthraquinone (200 mg, 0.24 mmol), urea (8 g, 133.3 mmol)
in DMF (5.5 mL) was refluxed for 14-18 h. A mixture of toluene (50 mL) and water (50 mL)
was then added, the organic layer was separated, dried over MgSO , solvent was evaporated in
4
vacuum by rotary. The crude product was purified by column chromatography on alumina
(elution with petroleum ether - toluene). Subsequent recrystallization gave pure compounds.
2
,7-Bis(4-(octyl(phenyl)amino)phenyl)naphtho[4,3,2,1-lmn][2,9]phenanthroline (8a). Yield 60
1
mg (31%), mp 164-165 ºC (petroleum ether - toluene). H NMR (CDCl , 400 MHz) δ: 0.89 (6H,
3
t, J 6.9 Hz, 2Me), 1.34 (20H, m, 2(CH ) ), 1.76 (4H, m, 2CH ), 3.81 (4H, t, J 7.7 Hz, 2NCH ),
2
5
2
2
7
.10 (6H, m, H ), 7.21 (4H, d, J 7.7 Hz, H ), 7.37 (4H, m, H ), 7.92 (2H, m, H ), 8.13 (2H, s,
Ar Ar Ar Ar
1
3
H ), 8.36 (6H, m, H ), 9.60 (2H, m, H ) ppm. C NMR (CDCl , 100 MHz) δ: 14.27, 22.81,
Ar
Ar
Ar
3
2
7.30, 27.68, 29.49, 29.61, 31.99, 52.63 (2C H ), 114.75 (2CH), 116.59 (2C), 118.46 (4CH),
8 17
1
23.10 (2CH), 123.85 (4CH), 125.25 (2C), 128.53 (4CH), 129.21 (2CH), 130.28 (2CH), 131.21
(2C), 133.36 (2C), 136.54 (2C), 146.64 (2C), 147.74 (2C), 149.20 (2C), 153.91 (2C) ppm.
Found: C, 85.84; H, 7.24; N, 6.96%; C H N C, 85.67; H, 7.44; N, 6.89%.
58
60
4
2
,8-Bis(4-(octyl(phenyl)amino)phenyl)benzo[de]isoquino[1,8-gh]quinoline (9a). Yield 75 mg
1
(
37%), mp 204-205 ºC (petroleum ether - toluene). H NMR (CDCl , 400 MHz) δ: 0.89 (6H, t, J
3
8

ACCEPTED MANUSCRIPT
6
.9 Hz, 2Me), 1.32 (20H, m, 2(CH ) ), 1.74 (4H, m, 2CH ), 3.78 (4H, t, J 7.7 Hz, 2NCH ), 7.08
2 5 2 2
(
6H,m, H ), 7.17 (4H, d, J 7.7 Hz, H ), 7.35 (4H, t, J 7.5 Hz, H ), 7.76 (2H, m, H ), 7.83 (2H,
Ar Ar Ar Ar
t, J 7.5 Hz, H ), 7.92 (2H, s, H ), 8.18 (2H,d, J 8.7 Hz, H ), 9.00 (2H, d, J 7.7 Hz, H ) ppm.
Ar
Ar
Ar
Ar
1
3
C NMR (CDCl , 100 MHz) δ: 14.25, 22.80, 27.30, 27.67, 29.48, 29.60, 31.98, 52.61 (2C H ),
3
8
17
1
15.02 (2CH), 118.91 (4CH), 122.72 (2CH), 123.32 (4CH), 123.41 (2C), 123.96 (2C), 127.97
4CH), 128.58 (2CH), 129.58 (4CH), 130.96, (2CH), 131.10 (2C), 132.99 (2C), 137.85 (2C),
47.87 (2C), 148.90 (2C), 150.12 (2C), 151.63 (2C) ppm. Found: C, 85.33; H, 7.09; N, 6.87%;
(
1
+
+
C H N C, 85.67; H, 7.44; N, 6.89%. HMRS, found: [M+H] m/z 812.4820 C H N [M+H]
58
60
4
58 60
4
8
12.4813.
Method B
2
,7-Bis(4-(octyl(phenyl)amino)phenyl)naphtho[4,3,2,1-lmn][2,9]phenanthroline (8a). Under
argon, a mixture of 1,4-diiodo-9,10-anthraquinone (700 mg, 1.52 mmol), the alkyne 4 (1.4 g,
.56 mmol), PdCl (PPh ) (20 mg, 0.028 mmol), CuI (10 mg, 0.052 mmol) in pyridine (20 mL)
4
2
3 2
о
was stirred and heated to 60 С. Then a hot solution of Na CO (550 mg, 5.1 mmol) in H O (8
2
3
2
mL) was added, and the mixture was refluxed for 0.5 h, after toluene (100 mL) was added. The
organic layer was separated, was washed with water (3×200 mL), dried over MgSO and
4
evaporated to dryness on rotary evaporator. Further urea (25 g, 0.42 mol) and DMF (18 mL)
were added, the mixture was refluxed for 18 h. Isolation and purification of compound were
analogous to the method A. Yield 265 mg (21.5%), mp 164-165 ºC (petroleum ether - toluene).
Method C
A mixture of diiodo-9,10-anthraquinone (1.4 g, 3.0 mmol) and copper acetylide 5 (1.2 g, 7.0
o
mmol) in pyridine (25 mL) was stirred under stream of argon at 60-65 C for 0.5 h. Then ethyl
acetate (200 mL) was added, the organic layer was washed with 5 % aqueous NH (100 mL) and
3
water (300 mL), dried over MgSO and evaporated to dryness on rotary evaporator. Further urea
4
(30 g, 0.5 mol) and DMF (21 mL) were added, the mixture was refluxed for 1-3 h. Isolation and
purification of compounds were analogous to the method A.
9

ACCEPTED MANUSCRIPT
2
,7-Di(thien-2-yl)naphtho[4,3,2,1-lmn][2,9]phenanthroline (8b). Yield 350 mg (28%), mp
1
2
55-256 ºC (toluene). H NMR (DMSO-D , 400 MHz) δ: 7.24 (2H, dd, J 3.6, 5.1 Hz, H ), 7.52
6
Ar
(
2H,dd, J 1.2, 5.1 Hz, H ), 7.90 (2H, dd, J 1.2, 3.6 Hz, H ), 7.94 (2H, m, H ), 8.07 (2H, d, J
Ar Ar Ar
1
3
1
.5 Hz, H ), 8.24 (2H, d, J 1.5 Hz, H ), 9.48 (2H, m, H ) ppm. C NMR (DMSO-D , 100
Ar Ar Ar 6
MHz) δ: 114.75 (2CH), 116.14 (2C), 124.65 (2CH), 126.05 (2CH), 128.87 (2CH), 129.23
2CH), 129.98 (2CH), 130.86 (2CH), 132.00 (2C), 136.50 (2C), 145.20 (2C), 145.47 (2C),
(
1
49.34 (2C) ppm. Found: C, 74.78; H, 3.30; N, 6.70; S, 15.47%; C H N S C, 74.61; H, 3.37;
26 14 2 2
N, 6.69; S, 15.32%.
2
,8-Di(thien-2-yl)benzo[de]isoquino[1,8-gh]quinoline (9b). Yield 420 mg (34%), mp 329-
1
3
30 ºC (pyridine). H NMR (DMSO-D , 400 MHz) δ: 7.27 (2H, dd, J 3.6, 5.0 Hz, H ), 7.73
6 Ar
(
2H, dd, J 1.0, 5.1 Hz, H ), 7.99 (4H, m, H ), 8.09 (2H, d, J 7.8 Hz, H ), 8.37 (2H, s, H ),
Ar Ar Ar Ar
8
.86 (2H, dd, J 0.9, 7.2 Hz, H ) ppm. Found: C, 74.38; H, 3.37; N, 6.73; S, 15.21%;
Ar
C H N S C, 74.61; H, 3.37; N, 6.69; S, 15.32%.
26
14
2 2
X-ray crystal structure analysis for compound 8b
Formula: C H N S , M = 418.51, yellow crystal, monoclinic, space group; P2 /c, a =
2
6
14
2
2
r
1
3
1
1
2.0189(6), b = 7.7609(4), c = 21.7992(11) Å, β = 105.817(2)º, V = 1956.38(17) Å , Z = 4, D =
c
3
-1
3
.421 g/cm , µ = 0.288 mm , crystal size 0.02 × 0.08 × 0.58 mm , 4729 independent reflections
were collected, wR = 0.1675, S = 1.06 for all reflections, the final R index was 0.0507 for 3426
2
F > 4σ).
X-ray crystal structure analysis for compound 9b
Formula: C H N S , M = 418.51, red crystal, orthorhombic, space group, Pbca, a =
2
6
14
2
2
r
3
3
1
7.3336(5), b = 10.7758(4), c = 20.3308(7) Å, V = 3797.5(2) Å , Z = 8, D = 1.464 g/cm , µ =
c
-1
3
0
.297 mm , crystal size 0.06 × 0.18 × 0.41 mm , 4447 independent reflections were collected,
wR = 0.1639, S = 1.06 for all reflections, the final R index was 0.0482 for 3378 F > 4σ).
2
1
0

ACCEPTED MANUSCRIPT
CCDC 1475062 (8b) and 1475063 (9b) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data
Center via www.ccdc.cam.ac.uk/data_request/cif.
3
. Results and discussion
3
.1. Synthesis and characterization
The synthetic route for the diazabenzopyrenes 8 and diazaperylenes 9 is illustrated in Scheme
. The alkyne 4 was synthesized in several steps from diphenylamine. Initially alkylation of
1
diphenylamine with 1-bromooctane in aqueous NaOH solution in the presence of the BTEAC at
reflux led to N-octyldiphenylamine 1 with 87% yield. 4-Iodo-N-octyldiphenylamine 2 was
synthesized with 52% yield by iodination of compound 1 with I in aqueous KHCO solution
.
2
3
Then, the iodide 2 was subjected by Sonogashira reaction with 1-ethynylcyclopentanol to obtain
the alkynol 3 (yield 92%). The alkynol 3 was cleaved with alkali in toluene under reflux to the
alkyne 4 with 83% yield. Copper acetylide 5 was produced from 2-ethynylthiophene and CuCl in
aqueous solutions of NH , NH Cl, and NH OHꢀHCl with 94% yield. These conditions were not
3
4
2
suitable for preparation of copper acetylide from alkyne 4. For this reason, for the synthesis of
bis(R-ethynyl)-9,10-anthraquinones 6a, 7a the Sonogashira coupling reaction was used. The
bis(R-ethynyl)-9,10-anthraquinones 6b, 7b was synthesized by Castro–Stephens coupling
reaction. Synthesis of polycondensed compounds 8, 9 was based on heterocyclization of
bis(R-ethynyl)-9,10-anthraquinones with urea similar to that previously reported by us [28, 29].
That method allows using crude alkyne therefore the stages of cross-coupling and
heterocyclization are advisable to be carried out in a one-pot. The crude bis-alkyne 6a without
purification after Sonogashira coupling was cyclized to compound 8a (method B). Compounds
8
b and 9b were prepared via cyclization of the corresponding crude alkynes 6b and 7b after
Castro–Stephens coupling (Method C). It has been found that using R substituents with strong
donor properties decreases electrophilicity of reaction centers (C=O, C≡C), which results in
1
1

ACCEPTED MANUSCRIPT
deactivation of the bis-alkyne 6, 7 in the reaction with a nucleophile (urea). For example, the
time of cyclization of bis-alkynes 6a, 7a containing 4-(phenylamino)phenyl substituents was
significantly higher (19 h) than in the case of anthraquinones with propargyl and alkynyl
1
substituents (0.5 - 2 h). The compounds were characterized by elemental analysis, IR, H NMR,
1
3
C NMR and mass spectrometry. Crystals of heterocycles 8b, 9b we investigated by X-ray
analysis.
3
.2. Molecular structure and crystal packing of 8b and 9b
Crystals of 8b suitable for X-ray diffraction analysis were obtained by solvent evaporation
from toluene solution. Under these conditions compound 8b crystallized in centrosymmterical
P2 /c space group in a monoclinic system, with four molecules in one crystallographic unit cell
1
(Fig. 1). Compound 8b is asymmetrical with one thiophene ring reverted out of phenanthroline
plane by 13°. Also 8b forms π-stacked layers consisted of face-to-face dimers with π-π dimer
distance 3.382 Å and interdimer distance 3.427 Å following a “herringbone” packing of
neighboring layers. Two molecules in each dimer overlap through main conjugation backbone of
the molecule.
The molecules of 9b were packed with orthorhombic Pbca symmetry in a “herringbone”
layered structure (Fig. 2d). Both thiophene rings are twisted about ~5° to diazaperylene unit. In
contrast to 8b no π-π stacked dimers were observed but only separated dimers (Fig. 2b). These π-
π dimers have 3.544 Å interplanar distance (Fig. 2d). The dimers are shifted respectively each
other so that the intercentroid distance between thiophene ring of one dimer and benzene ring of
diazaperylene core of another dimer is 3.926 Å (Fig. 2c).
3
.3. Theoretical calculations
Quantum chemical calculations were used for theoretical study of frontier orbitals. For
compounds 8a and 9a the long octyl chain was replaced by methyl group (compounds 8a* and
1
2

ACCEPTED MANUSCRIPT
9
a*) to simplify the calculations and reduce influence of conformers. According to calculations
the torsion angle between benzene ring and heteroaromatic unit in 8a* and 9a* was found
approximately 22° and both molecules 8b and 9b were found to be completely flat. The frontier
molecular orbitals and their energy levels obtained by DFT calculations are shown in Fig. 3 and
Table S1. As can be seen from Fig. 3 for all substrates LUMO is mainly delocalized on the
electron deficient polycyclic heteroaromatic central unit and HOMO is delocalized along the
main conjugation chain of the molecule.
3
.4. Spectroscopic and electrochemical properties
For the synthesized molecules the energy levels of highest occupied molecular orbital
(
HOMO) and lowest unoccupied molecular orbital (LUMO) and HOMO-LUMO gaps (E or
g
opt
Eg ) were obtained from cyclic-voltammetry (CVA) experiments and from UV-vis absorption
and luminescence emission spectra (Table 1).
CVA revealed reversible oxidation peaks for 8a whereas other compounds demonstrate
irreversible and quasi-reversible oxidation peaks (Fig. 4). The irreversibility of the oxidation
peaks of thienyl-capped molecules (8b and 9b) could be due to the oxidative
electropolymerization processes which was demonstrated for thiophene containing compounds
[
39]. Reduction peaks were also observed for all compounds, and the LUMO levels was
estimated from reduction potentials correspondingly (Table 1).
For the toluene solutions of compounds 8 and 9 UV-vis absorption spectra and luminescence
emission spectra are presented in Fig. 5. The HOMO-LUMO gaps were obtained from the
intersection points of UV-vis absorption spectra and luminescence emission spectra as it was
found from Fig. 5. The characteristic values of molar absorption coefficients ε and luminescence
quantum yields ϕ for the investigated substances in toluene are presented in Table 1. The non-
substituted 1,7-diazaperylene has almost unity fluorescence quantum yield ϕ [40], however
substitution of 1,7-diazaperylene at 2,8-positions results in decrease of ϕ value.
1
3

ACCEPTED MANUSCRIPT
The optical and electrochemical properties which have been obtained for substances 6-9 are
available in Table S1, Supplementary Data. From the comparison of the HOMO-LUMO gaps
and the absorption coefficients of 1,8-diazabenzopyrenes 8 and 1,7-diazaperylenes 9 we can
observe that the 4-(phenylamino)phenyl groups not only decrease the HOMO-LUMO gaps but
also increase the absorption coefficients. A similar effect is produced by thienyl and phenyl [29]
substituents but its strength is smaller (see Table S1, Supplementary Data). This effect could be
caused by expansion of π-conjugation to the aromatic substituents with electron donor
properties.
The UV-vis and luminescence spectra of 8 and 9 in toluene have very similar lineshape to
those obtained in pure dioxane solution (Fig. S3, Supplementary Data) but luminescence spectra
of drop-casted films are shifted into the red region (Fig. 5).
In order to observe and discuss possible changes in the intensities and lineshapes of UV-vis
and luminescence spectra in conditions when solid-state aggregates are appearing, the spectra of
8
and 9 at mixtures of water and dioxane were measured with different water concentrations
(Fig. S3, Supplementary Data). The luminescence bands of 8 and 9 in solid states and in
dioxane/water mixtures at high water concentrations revealed close similarity. The substances 8
and 9 have low solubility in water and aggregates of the molecules are expected in dioxane/water
mixtures, so at these mixtures the solid-state luminescence is probably observed. The similar
approach was presented in the works [41, 42] to observe solid-state luminescence of
diazabenzopyrenes and benzanthrones in solutions. The solid-state origin of luminescence of 8b
and 9b in dioxane/water solutions was confirmed by the luminescence lifetimes of 8b and 9b
which were obtained very similar for the solid states and the dioxane/water mixtures at high
water concentrations (Fig. S4 and Table S2 in Supplementary Data). In contrast, the
luminescence lifetimes of 8b and 9b in net dioxane strongly differ from those in the solid states
(Fig. S4 and Table S2 in Supplementary Data) which reveal the difference in origins of
1
4

ACCEPTED MANUSCRIPT
luminescence bands of 8b and 9b in solutions (in toluene or net dioxane) and in solid state (Fig.
S4, Supplementary Data).
4
. Conclusions
A simple and effective one-pot synthetic route was applied to obtain diaza-analogs of
benzopyrene and perylene containing thienyl and 4-(phenylamino)phenyl groups. The method
which demonstrated broad synthetic capabilities was tested in the preparation of polycondensed
molecules with substituents of different types (aliphatic, aromatic, heteroaromatic). For the
preparation of compounds with the desired substituents it is sufficient to use the appropriate
terminal alkyne on the stage of cross-coupling with diiodoanthraquinone. The 1,8-
diazabenzopyrenes 8 and 1,7-diazaperylenes 9 are convenient building blocks, which can be
used in the synthesis of the new small molecules, oligomers and copolymers. The strongest
effect was revealed when two diphenyl-amine substituents were bonded to the cores: decreasing
of HOMO-LUMO gaps and luminescence yields, and increasing of extinction coefficients were
observed. The solid-state luminescence was obtained for the synthesized substances in drop-
casted films and in solutions of dioxane and water mixtures. The obtained electrochemical,
optical and luminescent properties of new substances show possibility for their applications as
building units for semiconducting materials in organic electronics, and optical or luminescence
sensing devices.
Acknowledgments
This work was supported by the Russian Foundation for Basic Research (grants no. 15-03-
0
7682a, and no. 16-03-00082a) and the Ministry of Education and Science of the Russian
Federation. Authors would like to acknowledge the Multi-Access Chemical Service Center SB
RAS for spectral and analytical measurements.
1
5

ACCEPTED MANUSCRIPT
Appendix A. Supplementary data
Supplementary data related to this article can be found at
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0

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I
OH
i
H C
ii H C
17
8
iii H C
17
8
iv H C
17 8
1
7
8
NH
N
N
N
N
1
2
4
3
v
+
CuCl
S
S
Cu
R
5
R
O
O
I
I
O
N
vi or vii
viii
O
N
R
R
R
C H
8
17
6
8
R =
N
(a),
(b)
S
I
R
N
O
O
vi or vii
viii
O
O
N
I
R
R
9
7
Scheme 1. Reagents and conditions: i, C H Br, BTEAC, NaOH, H O, reflux, 24 h; ii, I ,
8
17
2
2
KHCO , H O, r.t., 2 h; iii, 1-ethynylcyclopentanol, PdCl (PPh ) , CuI, Na CO , Et NH, H O,
3
2
2
3 2
2
3
2
2
PhMe, 80 ºC, 3 h; iv, KOH, PhMe, reflux, 0.5 h; v, CuCl, NH Cl, NH , NH OHꢀHCl, H O, r.t., 5
4
3
2
2
h; vi, Alkyne 4, PdCl (PPh ) , CuI, Et N, PhMe, 75 ºC, 9 h; vii, copper acetylide 5, Py, 65 ºC,
2
3 2
3
0
.5 h; viii, (NH ) CO, DMF, reflux, 14-18 h.
2 2
2
1

ACCEPTED MANUSCRIPT
Fig. 1. Crystallographic data of compound 8b: the single-molecule (a), herring-bone packing in
the crystal (b), π-π interdimer distances (c), and the stacked dimers along b-axis (d).
Fig. 2. Crystallographic data of compound 9b: the single-molecule (a), the π-π stacked dimer
(b), the slippage/shift of dimers (c), herring-bone packing in the crystal, view along b+c (d).
2
2

ACCEPTED MANUSCRIPT
Fig. 3. HOMO, and LUMO orbitals for 8a*,b and 9a*,b with a 0.03 isocontour value
Fig. 4. Cyclic voltammetry plots of compounds 8, 9 measured in CH Cl solution. Potentials
2
2
+
calibrated vs Fc/Fc as an internal standard.
2
3

ACCEPTED MANUSCRIPT
Fig. 5. UV-vis absorption spectra (solid lines) and luminescence emission spectra of the
compounds 8 and 9 in toluene (dash lines), of drop-casted films (dot lines). The spectra were
normalized to match the intensity of long-wavelength maximum of absorption and short-
wavelength maximum of luminescence spectra.
2
4

ACCEPTED MANUSCRIPT
Table 1. Spectroscopic and electrochemical properties of compounds 8, 9 in solution.
abs
em
em
3
-1
-1
λ
max, nm λ max, nm λ max, nm ε, 10 M cm
a
a
a
g
opt, b
d
Compound EHOMO , eV ELUMO , eV E , eV
Eg , eV
ϕ
c
(
solution) (solution)
(solid)
(λ, nm)
8a
8b
9a
9b
-5.12
-5.52
-5.12
-5.72
-2.76
-2.84
-3.07
-3.22
2.36
2.68
2.05
2.50
2.74
2.82
2.41
2.57
384
491
443
561
489
543
74 (384)
0.10
0.08
0.15
0.5
346, 435
351, 478
315, 477
557
600
660
4.6 (435)
29 (450)
31 (477)
a
(
) Energies measured by CVA;
b
opt
(
) Eg estimated from the intersection point of UV-vis absorption spectrum and luminescence
emission spectrum in toluene;
c
(
) Extinction coefficients
ε
(at wavelengths which are specified in the brackets)
d
(
) Luminescence quantum yields in toluene solutions.
ϕ
2
5

ACCEPTED MANUSCRIPT
Highlights
1
,8-diazabenzopyrenes and 1,7-diazaperylenes were synthesized by one-pot process
The substances were characterized by CVA, UV-vis and luminescence spectroscopies
Possible applications: chemistry of polymers, organic electronics, sensors