Synthesis and characterization of new N-{4,6-bis[2-(het)arylvinyl]pyrimidin-2-yl}-substituted polycyclic aromatic imides

Article abstract of DOI:10.1007/s11172-019-2614-0

Two series of new N-{4,6-bis[2-(het)arylvinyl]pyrimidin-2-yl}-substituted aromatic polycyclic imides were synthesized. The synthesized chromophores were characterized by UV and fluorescence spectroscopy, cyclic voltammetry, and quantum chemical density functional theory calculations. A change in the nature of aryl (hetaryl) moieties was found to cause changes in the optical properties of both solutions of these compounds and thin films prepared from these compounds. The replacement of the phthalimide moiety by the 1,8-naphthalimide one has led to a significant increase in the lowest unoccupied molecular orbital energy.

Full text of DOI:10.1007/s11172-019-2614-0

1702
Russian Chemical Bulletin, International Edition, Vol. 68, No. 9, pp. 1702—1713, September, 2019
Synthesis and characterization of new
N-{4,6-bis[2-(het)arylvinyl]pyrimidin-2-yl}-substituted polycyclic aromatic imides
E. A. Komissarova,a,b A. N. Vasyanin, V. E. Zhulanov, I. V. Lunegov, E. V. Shklyaeva, and G. G. Abashev
b
b
b
b
a,b
aInstitute of Technical Chemistry, Ural Branch of the Russian Academy of Sciences,
3
ul. Akad. Koroleva, 614013 Perm, Russian Federation.
Tel.:+7 (342) 237 8289. E-mail: gabashev@psu.ru
b
Perm State University,
1
5 ul. Bukireva, 614990 Perm, Russian Federation.
Tel.: +7 (342) 239 6231. E-mail: ekaterina.komva@gmail.com
Two series of new N-{4,6-bis[2-(het)arylvinyl]pyrimidin-2-yl}-substituted aromatic poly-
cyclic imides were synthesized. The synthesized chromophores were characterized by UV and
fluorescence spectroscopy, cyclic voltammetry, and quantum chemical density functional
theory calculations. A change in the nature of aryl (hetaryl) moieties was found to cause
changes in the optical properties of both solutions of these compounds and thin films prepared
from these compounds. The replacement of the phthalimide moiety by the 1,8-naphthalimide
one has led to a significant increase in the lowest unoccupied molecular orbital energy.
Key words: phthalimide, 1,8-naphthalimide, pyrimidine, chromophore, quantum chemical
calculations.
Pyrimidine is a highly -deficient aromatic hetero-
promising small molecules as electron-deficient N-sub-
stituted polycyclic imides. The latter compounds are
utilized as semiconductor materials with electron conduc-
tivity and are employed in organic field-effect transis-
cycle and is often incorporated, as an efficient electron-
withdrawing moiety, into small molecules, oligomers,
1
—6
and polymers behaving as push-pull chromophores.
1
8—20
A π-conjugated system composed of this moiety and elec-
tron-donating aromatic carbo- and heterocycles linked by
a π-conjugated bridge causes an effective photoinduced
intramolecular charge transfer in the compound, giving
rise to fluorescence and nonlinear optical properties.
tors.
Most of these polycyclic imides bear an alkyl
substituent at the nitrogen atom, the presence of which
increases solubility of the compounds and, consequently,
improves their film-forming properties. Besides, the in-
troduction of alkyl substituents leads to the improvement
of conductivity because alkyl chains interact with each
other, thereby bringing the molecules in close proximity
4
,6-Bis[2-aryl(hetaryl)vinyl]-substituted pyrimidines
have been extensively studied since the early 2000s. These
compounds are described as pH sensors,5
,7,8
luminescent
and facilitating more efficient overlap of π-orbitals of
9
,10
18,19
materials for organic light-emitting diodes,
and mate-
conjugated moieties in the molecules.
N-Aryl- and
rials with nonlinear optical properties.9
,11
Pyrimidine
N-hetaryl-substituted polycyclic imides are much less
2
1—26
derivatives are also used as semiconductor layers in organic
studied.
Under ambient conditions, N-aryl-sub-
field-effect transistors.1
2—14
stituted naphthalene-1,4,5,8-tetracarboxylic or perylene-
3,4,9,10-tetracarboxylic acid diimides bearing 3-alkoxy-
1-phenyl-1,2,3,4-tetrahydroquinoline moieties at the
periphery were found to have both hole and electron
2
-Amino-4,6-dimethylpyrimidine is an important
starting compound for the preparation of the extended
π-conjugated systems exhibiting valuable properties, which
are of interest for organic electronics. This compound
contains reactive methyl groups, which can act as com-
2
7
conductivity at the ambient conditions. The simultane-
ous presence of electron-donating (carbazole, thiophene,
pyrrole) and electron-withdrawing (pyrimidine, phthal-
imide, 1,8-naphthalimide) moieties facilitates strong in-
tramolecular charge transfer, which has a direct effect on
optical and electrochemical properties. 1,8-Naphthalimides
containing both the electron-withdrawing pyridine ring at
the imide nitrogen atom and an electron-donating sub-
stituent at position 4 of the naphthalene ring exhibit in-
teresting optical properties, in particular, tuning fluores-
7
ponents in different condensation reactions, and an amino
group, which has both basic and nucleophilic properties
and, as a consequence, is capable of being involved into
the condensation reactions with aliphatic and aromatic
aldehydes, diazotization,15 alkylation, and acylation.
16
17
Besides, acid anhydrides and, in particular, cyclic dicarb-
oxylic acid anhydrides, are important acylating agents.
The use of these compounds allows to synthesize such
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1702—1713, September, 2019.
066-5285/19/6809-1702 © 2019 Springer Science+Business Media, Inc.
1

New polycyclic aromatic imides
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
1703
cence in different aggregated states.28 Therefore, the
synthesis of polycyclic imides containing different elec-
tron-donating carbo- and heterocyclic moieties are of
obvious interest.
meier—Haack reaction from 9-hexyl-9H-carbazole, which
was prepared by the alkylation of carbazole with 1-bromo-
3
4
hexane in DMF in the presence of NaOH. The heating
of 2-amino-4,6-dimethylpyrimidine 1 with phthalic and
1,8-naphthalic anhydrides at reflux in anhydrous DMF
under an argon atmosphere afforded 2-(4,6-dimethyl-
Previously, we synthesized and characterized sym-
metrical and unsymmetrical 4,6-bis[2-(het)arylvinyl]-
pyrimidines bearing electron-donating alkoxy- and alkyl-
mercapto substituents at position 2 of the pyrimidine
2
6
pyrimidin-2-yl)phthalimide (2) described earlier and
2-(4,6-dimethylpyrimidin-2-yl)-1,8-naphthalimide (3)
(Scheme 1). Previously, 2-(4,6-dimethylpyrimidin-2-yl)
phthalimide (also referred to as 2-(4,6-dimethylpyrimidin-
2-yl)isoindoline-1,3-dione) was synthesized by heating
the same starting compounds at reflux in a minimum
2
9—32
ring.
The goal of this work is to synthesize Y-shaped
D—π-A—π-D-type chromophores, which contain aro-
matic imide (phthalimide or 1,8-naphthalimide) attached
through its nitrogen atom to atom C(2) of the pyrimidine
ring as the electron-withdrawing core, investigate the
optical and electrochemical properties of the synthesized
compounds, and determine the energy characteristics of
the molecules by experimental methods and quantum
chemical calculations.
2
6
amount of toluene at 200C.
The condensation of N-acylated 4,6-dimethylpyrimid-
ines 2 and 3 with appropriate carbaldehydes in a 5 M
aqueous NaOH solution in the presence of the phase-
3
5
transfer catalyst Aliquat 336 gave target conjugated
pyrimidines 4—11 (see Scheme 1). These compounds are
D—π-A—π-D-type chromophores containing a combina-
tion of pyrimidine and aromatic imide moieties linked
together through the imide nitrogen atom, as the electron-
withdrawing core.
Results and Discussion
The target compounds were synthesized as follows.
First, the main starting compound, viz., 2-amino-4,6-
dimethylpyrimidine (1), was prepared by the cyclo-
condensation of acetylacetone with urea.33 9-Hexyl-9H-
carbazole-3-carbaldehyde was synthesized by the Vils-
All Y-shaped pyrimidines 2—11 were synthesized in
high yields (68—85%) and were isolated and purified by
silica gel column chromatography. The structures of all
Scheme 1
Reagents and conditions: i. DMF, reflux, 24 h, argon atmosphere; ii. ArCHO, Aliquat 336, 5 M NaOH, reflux, 5 h, argon atmosphere.

170 4
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
Komissarova et al.
O(2)
C(5)
C(3)
C(13A)
C(6)
C(7)
C(4)
N(1)
C(12A)
C(13)
N(3)
C(11A)
C(12)
N(3A)
C(9)
C(2)
O(1A)
C(8)
C(10)
C(9A)
C(1)
C(14A)
C(11)
N(1A)
C(10A)
N(2)
C(1A)
O(1)
C(2A)
N(2A)
C(8A)
C(14)
O(2A)
C(4A)
C(7A)
C(3A)
C(6A)
C(5A)
Fig. 1. Crystal structure of compound 2 (CCDC 1883703) with thermal ellipsoids drawn at the 50% probability level.
compounds were confirmed by H and 13C NMR spectro-
scopy and elemental analysis. Chromophores 2—11 are
readily soluble in common organic solvents. For chromo-
phores 2 and 3, we obtained crystals suitable for X-ray
diffraction. Compounds 2 and 3 have the same molecular
geometry. Compound 2 crystallizes in the centrosym-
metric triclinic space group. There are two crystallo-
graphically independent molecules of compound 2 with
similar geometry per asymmetric unit (Fig. 1). All bond
lengths and most bond angles fall within the normal ranges
1
ometry per asymmetric unit (Fig. 4). The 1,8-naphth-
alimide moiety and the pyrimidine ring are planar within
0.006 and 0.003 Å, respectively. The dihedral angles be-
tween the planes of the 1,8-naphthalimide moiety and the
pyrimidine ring in two independent molecules are 78.0
and 82.8. The crystal packing of compound 3 is shown
in Fig. 5. In the crystal, the molecules are arranged in an
antiparallel fashion. The π—π interaction between the
antiparallel layers is observed at a distance of 3.59 Å. The
planes of the 1,8-naphthalimide moieties of two crystal-
3
6
indicated by Mercury Mogul Geometry Check. The
pyrimidine and phthalimide moieties in compounds 2 and
3
are planar within ~0.002 Å. The dihedral angles between
the planes of the pyrimidine and phthalimide moieties of
two independent molecules are 57.9 and 69.5. The crys-
tal packing of compound 2 is shown in Figs 2 and 3. It can
be seen that there is π—π conjugation between the pyr-
imidine rings. The distances between the centroids of
the phthalimide moieties of two identical molecules are
0
b
3.959
3
.282
6
.657
3
.71 and 4.08 Å; the distances between the planes of
two phthalimide moieties are 3.51 and 3.85 Å, respectively
see Fig. 3). The distance between phthalimide moiety
4.061
3
.959
(
3
.581
and the aromatic ring of the imide moiety of two indepen-
dent molecules is 3.95 Å. The distances between the
centroids of two aromatic rings of the imide moieties of
the identical molecules are 3.89 and 6.65 Å; the distances
between the planes of two imide moieties are 3.58 and 3.28 Å
3
.715
c
3.893
(see Fig. 2).
Fig. 2. Single crystal unit cell of compound 2 (general view).
Note. Figures 2, 3, 5, 6, and 9 are available in full color on the
web page of the journal (https://link.springer.com/journal/
volumesAndIssues/11172).
Compound 3 crystallizes in the centrosymmetric
monoclinic space group. There are two crystallographically
independent molecules of compound 3 with similar ge-

New polycyclic aromatic imides
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
1705
C(14A)
N(2A)
O(2A)
C(5A) C(3A)
C(6A)
C(7A)
C(4A)
C(10A)
C(11A)
C(8A)
C(2A) C(1A) N(1A)
O(1A) C(9A)
C(13A)
C(12A)
O(1)
C(8)
N(3A)
4.061
C(2)
C(12A)
C(11A)
N(3A)
C(1)
N(1) N(3)
C(9) N(2)
C(7)
C(13A)
C(9A)
N(1A)
O(1A)
C(1A) C(2A)C(8A)
C(10)
C(12)
C(13)
C(11)
3
.661
C(10A)
C(7A)
O(2A)
C(6)
C(4A)
C(5A)
C(3A)
C(6A)
C(14)
C(3)
C(4)
O(2)
C(5)
C(14A)
C(5)
3
.610
3
.715
C(4)
C(3)
O(2)
C(11) C(14)
C(13)
C(9)
N(2)
C(6)
C(7)
C(12) C(10) N(3) N(1)
C(1)
C(2)
C(8)
O(1)
C(14)
N(3)
C(13)
N(2)
C(9) N(1)
C(5)
C(6)
C(7)
O(2)
O(1)
C(4)
C(12)
C(11)
C(3)
C(10)
C(11)
C(1)
C(9)
C(2)
C(8)
N(1)
C(8)
C(2)
C(7)
C(6)
C(1)
C(12)
C(4) C(3)
O(1)
O(2)
C(5)
C(10) N(3)
C(14)
N(2)
C(13)
Fig. 3. Single crystal unit cell of compound 2 (detailed arrangement).
lographically independent molecules are inclined with
respect to each other by an angle of 5.5. The distance
between the centroid of the 1,8-naphthalimide moiety of
one independent molecule and the plane of the pyridine
ring of another independent molecule is 3.66 Å.
Cyclic voltammetry (CV) was used to study the electro-
chemical behavior of the synthesized compounds and
evaluate the frontier orbital energies. The cyclic volt-
ammograms of the compounds containing the phthalimide
moiety (2, 4—7) show three reduction peaks (Ered) at
O(2A)
C(10)
C(9)
C(15A)
C(6A)
C(2A)
N(1A)
C(16A)
C(17A)
C(14A)
C(18A)
N(3A)
O(1)
C(11)
C(12)
C(3A)
C(8)
C(7)
C(1A)
C(4A)
C(5A)
N(1)
C(13A)
N(2A)
C(13)
N(3)
C(12A)
C(11A)
C(7A)
C(1)
C(2)
C(17)
C(16)
C(6)
C(8A)
C(14)
C(18)
O(1A)
N(2)
C(4)
C(5)
C(3)
C(10A)
C(15)
C(9A)
O(2)
Fig. 4. Molecular structure of compound 3 (CCDC 1883705) with thermal ellipsoids drawn at the 50% probability level.

170 6
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
Komissarova et al.
b
c
a
b
3
.661
3
.590
3
.661
0
a
Fig. 5. Single crystal unit cell of compound 3.
–
0.86, –1.31, and –1.62 V (Fig. 6). The oxidation peaks
Substituted aromatic imides are used for the design of
materials with electron conductivity. It is generally as-
sumed that stable electron injection, high charge carrier
mobility, and resistance of organic semiconductors to air
oxidation require that the lowest unoccupied molecular
orbital (LUMO) energy is smaller than or equal to –4.0 eV.
The values of the ELUMO falling in the interval from –4.3
in the CV curves of compounds 4—7 are assigned to anodic
oxidation of electron-donating (thiophene, N-methyl-
pyrrole, N-hexylcarbazole, and p-tolyl) moieties of the
molecules resulting in dimers formation. The cyclic
voltammograms of almost all compounds bearing the
1
,8-naphthalimide moiety (8—11), except for com-
1
8,37
pound 3, show one broadened reduction peak at –1.6 V.
to –4.4 eV are treated to be the most preferable.
To
The oxidation peaks (E ) also correspond to oxidation of
electron-donating moieties of the molecules (Fig. 7).
achieve this electron affinity, electron-withdrawing groups
should be introduced into the structure of the expected
ox
I/mA
.0
1
0
.5
–
2.0
–1.5
–1.0
–0.5
0
0.5
1.0
1.5
E/V
–
–
–
–
–
–
0.5
1.0
1.5
2.0
2.5
3.0
I/mA
0
0
0
0
0
.9
.7
.5
.3
.1
2
4
5
6
7
–
1
1
E/V
–
0.1
Fig. 6. CV curves of pyrimidines 2 and 4—7.

New polycyclic aromatic imides
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
1707
I/мА
0
0
.7
.2
0
–
2.0
–1.5
–1.0
–0.5
0.5
1.0
I/мА
1.5
E/V
–
–
0.3
0
.20
0.8
0
.15
–
1.3
3
8
9
0.10
0.05
0
–1.8
–
2.3
–
2
2 E/V
1
1
0
1
–
0.5
1.0
–
Fig. 7. CV curves of pyrimidines 3 and 8—11.
semiconductor as substituents at nitrogen or carbon atoms
in the aromatic core of polycyclic imide. The embedding
of the pyrimidine ring into the structure of any conjugated
molecule generally leads to a decrease in the LUMO en-
ergy, which, in turn, facilitates high electron mobility. For
the synthesized pyrimidines, the highest occupied mo-
lecular orbital (HOMO) and LUMO energies for com-
pounds 2 and 3 are –6.22/–4.16 eV and –6.45/–3.77 eV,
respectively (Table 1). An increase in the conjugation
length of chromophores 4—11 by introducing 2-aryl-
Therefore, the LUMO level of the target products can
be tuned by changing the nature of the substituent at
position 2 of the pyrimidine ring. The LUMO energy
for 4,6-disubstituted pyrimidin-2-yl-1,8-naphthalimides
8—11 is in the range from –3.98 to –3.80 eV; for 4,6-di-
substituted pyrimidin-2-yl-phthalimides 4—7, the LUMO
energy ranges from –4.38 to –4.23 eV (see Table 1). These
Table 1. The HOMO/LUMO energies and band gaps (Egelc)
of compounds 2—11, which were experimentally determined
(
hetaryl)vinyl substituents at positions 4 and 6 of the
(
I) and calculated (II)
pyrimidine ring leads to a change in the energy character-
istics of the molecules, in particular, to a decrease in the
band gap width. The presence of both phthalimide and
Com-
pound
Ia
IIb
EHOMO ELUMO Egelc EHOMO ELUMO Egelc
1
,8-naphthalimide moieties leads to an increase in the
ionization potential (EHOMO) for the carbazole- and
pyrrole-containing chromophores (5, 7, 9, 11), the LUMO
energy being decreased. This also causes a decrease in the
eV
2
3
4
5
6
7
8
9
–6.22
–6.45
–6.23
–5.92
–6.25
–5.72
–6.03
–5.81
–6.10
–5.92
–4.16
–3.77
–4.27
–4.28
–4.23
–4.38
–3.92
–3.95
–3.98
–3.80
2.06 –7.43
2.68 –6.91
1.96 –6.23
1.64 –5.86
2.02 –6.18
1.34 –5.56
2.11 –6.20
1.86 –5.85
2.12 –6.16
2.12 –5.54
–2.20
–2.48
–2.24
–2.25
–2.40
–2.17
–2.41
–2.45
–2.44
–2.44
5.26
4.42
3.99
3.61
3.78
3.39
3.79
3.39
3.72
3.10
elc
band gap width (Eg ), particularly in compounds 5, 7,
and 9 (see Table 1). The highest occupied molecular orbital
energy (EHOMO) for compounds 5, 7, 9, and 11 varies from
–
5.92 to –5.72 eV. The HOMO energies (EHOMO) of
tolyl- and thiophene-substituted N-pyrimidin-2-ylphthal-
imides 4 and 6 are –6.23 and –6.25 eV, respectively, which
are only slightly lower than the corresponding value de-
termined for the starting 4,6-dimethylpyrimidin-2-yl-
phthalimide 2 (–6.22 eV). The average electron affinity
10
11
a
The values were determined from the CV curves:
(
also referred to as ELUMO) for 4,6-disubstituted pyrimid-
ox
+
EHOMO(eV) = –(E
+ 4.80), ELUMO(eV) =
Eg (eV) = EHOMO –
onset vs Fc/Fc
41,42
in-2-yl-1,8-naphthalimides 8—11 is –3.9 eV; for related
compounds 4—7 bearing the phthalimide moiety, this
parameter is in the range from –4.38 to –4.23 eV.
red
elc
=
–(E
+ 4.80);
onset vs Fc/Fc+
– ELUMO;
b
quantum chemical calculations.

1708
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
Komissarova et al.
LUMO
HOMO
2
3
Fig. 8. Electron density distribution in the molecules of compounds 2 and 3.
LUMO energies are typical for materials with electron
conductivity.3
ring and the vinyl carbon atoms directly bonded to this
ring. In compounds 4 and 6, the LUMO electron density
is distributed along the conjugation chain and is present
also on the terminal p-tolyl (4) and thiophene (6) moieties.
In compounds 8—11, the LUMO electron density is
completely concentrated on the 1,8-naphthalimide moi-
eties of the molecules (see Fig. 9).
7
The geometric and electronic structures of the synthe-
sized compounds were studied in the gas phase by quantum
chemical calculations at the PBE0-D3/Def2-TZVPD level
of theory using the Firefly program38 partially based on
the original GAMESS (US) source code.39 The calcula-
tions showed that the electron density of HOMO and
LUMO in compound 2 is located on the pyrimidine and
phthalimide rings, respectively. In pyrimidine 3, the
HOMO electron density is concentrated in the naphtha-
lene ring of the 1,8-naphthalimide moiety; the LUMO
electron density — in the 1,8-naphthalimide moiety (Fig. 8).
The calculated HOMO energies of chromophores
The optical properties of pyrimidines 2—11 were stud-
ied by UV and fluorescence spectroscopy (Figs 10—13).
The optical characteristics of substituted phthalimides
4—7 and substituted 1,8-naphthalimides 8—11 vary de-
pending on the nature of the aryl or hetaryl moiety.
Compounds 4—11 absorb in the region from 310 to
505 nm, which corresponds to the intramolecular charge
transfer from the electron-donating hetaryl moiety to the
electron-withdrawing core (see Figs 10 and 12). The ab-
sorption band maxima of chromophores 5 and 9 and also
of 7 and 11 containing the N-hexylcarbazole and N-methyl-
pyrrole moieties, respectively, undergo a bathochromic
shift with respect to the absorption band maxima in the
spectra of p-tolyl- and thiophene-containing chromo-
phores 4, 6, 8, and 10. The emission spectra (see Figs 11
and 13) show that chromophores 4 and 6 and also 8 and
10 exhibit fluorescence in the blue region, whereas chro-
mophores 5 and 9 and also 7 and 11 show fluorescence in
the yellow region.
3
—11 are in good agreements with the corresponding
experimental characteristics (see Table 1), whereas the
calculated LUMO energies significantly differ from the
parameters determined from electrochemical measure-
ments. We believe that the most reasonable prediction of
the band gap width between HOMO and LUMO can be
made based on calculations of the vertical transition energy
from the ground state S to the excited state S (the verti-
0
1
cal excitation energy, S —S ). This way of determination
0
1
of the band gap width is more physically meaningful com-
pared to calculations directly from the energy difference
between the HOMO and LUMO eigenvalues.40
The HOMO electron density in compounds 4—11 is
located on the π-conjugated system composed of 2-aryl-
The relative fluorescence quantum yield increases in
the series of compounds 4—7 bearing the phthalimide
moiety in the order 6 < 7 < 4 < 5; the same pattern is
observed for the compounds containing the 1,8-naphth-
alimide moiety (10 < 11 < 8 < 9). The highest mo-
lar absorption coefficients (ε) are observed for solu-
tions of the compounds containing the carbazole moiety
(
hetaryl)vinyl moieties and the C(4), C(5), and C(6) atoms
of the pyrimidine ring (Fig. 9). In compound 7, the LUMO
electron density is completely located on the phthalimide
moiety. In compound 5, the LUMO electron density is
concentrated also at the nitrogen atoms of the pyrimidine

New polycyclic aromatic imides
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
170 9
LUMO
HOMO
4
5
6
7
LUMO
HOMO
8
9
10
11
Fig. 9. Electron density distribution in the HOMO and LUMO in the molecules of compounds 4—11.
A
I (arb. units)
.0
1
0
1
0
0
0
0
.0
.8
.6
.4
.2
4
5
6
7
4
5
6
7
.8
0.6
0.4
0.2
5
10
710 /nm
600
800 /nm
Fig. 10. Electronic absorption spectra of solutions of compounds
Fig. 11. Emission spectra of solutions of compounds 4—7 in THF
—7 in THF (C = 1•10– mol L ).
5
–1
(C = 1•10 mol L ) at ex of 380 (4, 6), 500 (5), and 430 nm (7).
–6
–1
4

1710
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
Komissarova et al.
Table 2. Optical characteristics of compounds 2—11
Compound
mахabs/nm (ε/L mol–1 cm–1
)
mахem
onset
Egabs/eV
Δν/cm–1
ΦF
nm
а
2
3
4
5
6
7
8
9
290 (11150)
473
372
454
570
450
560
450
567
448
560
390
375
480
555
482
556
480
526
480
563
3.17
3.31
2.58
2.23
2.57
2.23
2.58
2.35
2.58
2.20
—
0.097b
330 (15870), 340 (14280)
312 (17860), 375 (18850)
420 (36900), 475 (34450)
325 (16481), 387 (16219)
408 (24200), 500 (22350)
2530
4640
3509
4446
2143
4444
3595
3385
1944
0.048
а
0.35
c
0.43
а
0.08
d
0.21
а
320 (29250), 348 (26050), 375 (22550)
374 (39500), 471 (41300)
0.36
c
0.39
а
1
1
0
1
325 (18210), 389 (19030)
310 (8650), 505 (28300)
0.12
d
0.20
Notes: mахabs is the absorption band maximum, ε is the molar absorption coefficient, 
is the onset absorption
onset
em
abs
wavelength in the red region, mах is the emission band maximum, E
is the optical band gap calculated by the
g
–
1
7
abs
em
formula 1240/λonset, Δν is the Stokes shift (cm ) calculated by the formula 10 (1/λ
– 1/λmах ), ΦF is the
mах
fluorescence quantum yield, which was determined using the following compounds as the standard: for compounds
4
3
2
(
, 4, 8, and 10, aminophthalimide in EtOH (Φ = 0.6,  = 380 nm); for compound 3, quinine sulfate in 0.1 N H SO
F ex 2 4
Φ = 0.55, ex = 340 nm);44 for compounds 5 and 9, rhodamine B in EtOH (Φ = 0.65,  = 500 nm); for com-
pounds 7 and 11, rhodamine B in EtOH (Φ = 0.65,  = 490 nm).
45
F ex
4
5
F
ex
I (arb. units)
.0
A
1
1
0
0
0
0
.0
.8
.6
.4
.2
8
9
1
1
8
9
1
1
0
0
0
0
.8
.6
.4
.2
0
1
0
1
6
00
800 /nm
4
90
690 /nm
Fig. 13. Emission spectra of solutions of compounds 8—11 in
THF (C = 1•10 mol L ) at ex of 380 (8, 10), 400 (9), and
505 nm (11).
–
6
–1
Fig. 12. Electronic absorption spectra of solutions of compounds
5
–1
8
—11 in THF (C = 1•10– mol L ).
(
34450 L mol–1 cm–1 for 5 and 41050 L mol–1 cm–1 for 9).
naphthalimide core linked to electron-donating aromatic
carbo- or heterocyclic moieties by the vinyl bridge. The
A comparison of the optical characteristics of the com-
pounds bearing the same aryl(hetaryl) groups but different
imide moieties demonstrates that their properties are very
similar (Table 2), except for the starting compounds 2 and 3.
Thin films on quartz plates were prepared from solu-
tions of compounds 4—11 in chlorobenzene by the centri-
fugation (spin-coating technique) in an argon-filled
Glovebox system. The spectroscopic characteristics of the
films of pyrimidines confirm the patterns of changes in the
optical properties, which were observed for solutions of
these chromophores in THF (Table 3, Figs 14 and 15).
In summary, we synthesized and characterized two
series of D—π-A—π-D chromophores, which consist of
the electron deficient 2-(4,6-dimethylpyrimidin-2-yl)-
phthalimide or 2-(4,6-dimethylpyrimidin-2-yl)-1,8-
Table 3. Optical characteristics of films of chromophores 4—11
Com-
pound
λmахabs λmахem
nm
λonset
Egopt/eV Δν/cm–1
4
5
6
7
8
9
396
416
370
405
385
410
370
430
530
610
460
606
530
600
500
660
480
600
460
602
470
580
500
560
2.50
2.07
2.58
2.06
2.64
2.14
2.48
2.21
6385
7645
5333
8190
7107
7724
7027
8104
1
1
0
1

New polycyclic aromatic imides
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
1711
I (arb. units)
silane as the internal standard. The signals of protons are de-
noted as follows: pyrimidine ring, Pyrim; pyrrole ring, Pyr;
thiophene ring, Th; carbazole moiety, Cz; phthalimide, PI;
1
0
0
0
0
.0
.8
.6
.4
.2
4
5
6
7
1
,8-naphthalimide, NPI. The IR spectra were measured on
a SpectrumTwo FTIR spectrometer (Perkin-Elmer).
The X-ray diffraction data sets were collected at 295(2) К on
an X-calibur 3 single-crystal X-ray diffractometer (Oxford
Diffraction) using monochromatic Mo-K radiation (0.71073 Ǻ)
and a graphite monochromator. The structures were solved by
direct methods with the SHELXS-90 program package (Sheldrick,
1
990) and refined by the least-squares method with the SHELXL-97
program package (Sheldrick, 1997). The crystallographic data
for compound 2: C14H11N O , M = 253.26, triclinic,
3
2
a = 8.2270(19) Å, b = 12.1529(18) Å, c = 14.282(2) Å,
5
00
600
700
800 /nm
 = 110.285(14),  = 102.620(20),  = 98.738(17),
–
3
V = 1265.9(4) Å , T = 295(2), space group P1, Z = 4, (Mo-Kα) =
Fig. 14. Emission spectra of films of compounds 4—7.
–
1
=
0.092 mm . The final refinement parameters: R = 0.0543,
1
wR = 0.1264 (for 3820 reflections with I > 2σ(I)); R = 0.0890,
2
1
I (arb. units)
wR2 = 0.1530 (for a total of 5872 independent reflections,
Rint = 0.0279), S = 1.027. The maximum and minimum residu-
1
0
0
0
0
.0
.8
.6
.4
.2
-
3
al electron density peaks are 0.189 and –0.242 e Å , respec-
8
9
1
1
tively. The crystallographic data for compound 3: C18H13N O ,
3
2
M = 303.31, monoclinic, a = 14.360(3) Å, b = 13.458(3) Å,
3
c = 16.107(4) Å,  = 110.21(3)°, V = 2921.1(13) Å , T = 295(2),
–
1
space group P2 /c, Z = 8, (Mo-K) = 0.093 mm . The final
1
0
1
refinement parameters: R1 = 0.0593, wR2 = 0.1347 (for 4111
reflections with I > 2σ(I)); R1 = 0.1076, wR2 = 0.1654 (for
a total of 6988 independent reflections, Rint = 0.0295), S = 1.022.
The maximum and minimum residual electron density peaks are
–
3
0
.241 and –0.215 e Å , respectively.
Elemental analysis was performed using a CHNS-932 LECO
Corp analyzer. The melting points were determined with Mettler
Toledo MP 70 and NETZSCH DSC 214 Polyma DSC21400A-
0
115-L apparatuses. Fluorescence spectra were recorded on
a Shimadzu RF-5301pc spectrofluorometer. The cell size was
6
00
800 /nm
–6
–5
–1
1
010 mm, the concentrations of solutions were 10 —10 mol L
.
Fig. 15. Emission spectra of films of compounds 8—11.
The relative quantum yields were calculated using a procedure
4
4
described in the monograph for three—five solutions of each
–
6
–7
–1
compound at concentrations of 10 —10 mol L . The UV
LUMO energy of 4,6-disubstituted pyrimidin-2-yl-1,8-
naphthalimides varies in the range from –3.98 to –3.80 eV;
for 4,6-disubstituted pyrimidin-2-ylphthalimides, the
LUMO energy is from –4.38 to –4.23 eV. These com-
pounds can be considered as semiconductors with electron
conductivity. The presence of N-hexylcarbazole and
N-methylpyrrole moieties in the chromophore structure
leads to a red shift of the absorption and fluorescence
maxima wavelengths in THF solutions and to the increase
of the molar absorption coefficient and fluorescence quan-
tum yield. The fluorescence maxima were found to strongly
depend on the nature of the aryl(hetaryl) moiety. Thus,
the thiophene-containing chromophores exhibit fluores-
cence in the blue region; the chromophores bearing p-tolyl
moieties, in the green region; the chromophores containing
strong electron-donating moieties (carbazole, N-methyl-
pyrrole), in the orange region.
spectra were recorded on a UV-2600 UV-VIS spectrometer
–1
(
Shimadzu), the concentration of the solutions was 10–5 mol L
.
The spectra were processed with the UV Probe 2.42 software and
the Panorama 3.1 Fluorescence.
The course of the reactions was monitored and the purity of
the compounds was checked by TLC on Sorbfil plates. The
mixtures were separated and the target products were purified on
a column packed with silica gel (Lancaster, silica gel 60,
0.060—0.2 mm) using eluents, which were chosen by means of
TLC. Electrochemical studies were carried out on a Potentiostat/
Galvanostat/ZRA Interface 1000 instrument in a conventional
three-electrode cell using an ITO electrode (glass plates coated
on their inwardly facing surfaces with a conductive indium—tin
oxide layer, R = 8—12 Ohm, Aldrich) as the working electrode,
s
platinum wire as the auxiliary electrode (ERL-02), the silver
chloride reference electrode (EVL-1M4), ~20 °C. A 4 : 1
CH CN—CH Cl mixture (10 mL) was used as the solvent;
3
2
2
+
–
–
(C H ) N ClO was used as ClO the background electrolyte,
Cbackground = 0.1 mol L , Ccompound = 1•10 mol L ; the
potential scan rate was Vscan = 100 mV s . The cyclic voltam-
metry data were processed with the Gammy Instruments Frame-
work Date Acquisition Version 6.25; the curves were construct-
ed using Microsoft Excel tools (2007, 2013). Quantum chemical
2
5 4
4
4
–
1
–3
–1
–
1
Experimental
The H and 13C NMR spectra were recorded on a Bruker
1
AvanceNeo III HD spectrometer (400 MHz) with tetramethyl-

1712
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
Komissarova et al.
calculations were performed at the PBE0-D3/Def2-TZVPD
level of theory in the gas phase with he Firefly program partially
based on the original GAMESS (US) source code using a PSU-
Kepler supercomputer.
The following commercial reagents were used: p-toluic al-
dehyde (AlfaAesar), thiophene-2-carbaldehyde (AlfaAesar),
N-methylpyrrole-2-carbaldehyde (AlfaAesar), phthalic anhydride
J = 8.4 Hz); 8.13 (d, 2 H, PI, J = 7.6 Hz); 8.35 (m, 4 H, Cz, 2 CH=).
1
3
C NMR (CDCl ), δ: 13.9, 22.5, 26.9, 28.9, 31.5, 43.3, 107.3,
3
109.0, 119.3, 120.2, 120.5, 122.9, 123.3, 123.6, 125.4, 126.0,
127.2, 137.3, 140.9, 141.1, 163.0, 164.3 (overlapping of signals).
N-{4,6-Bis[(E)-2-(thiophen-2-yl)ethenyl]pyrimidin-2-yl}-
phthalimide (6). Yellow crystalline compound. Yield 30 mg (75%),
m.p. 142.3 C. Found (%): C, 64.98; H, 3.30; N, 9.01; S, 14.27.
(
AlfaAesar), and 1,8-naphthalic anhydride (AlfaAesar).
C24H15N O S . Calculated (%): C, 65.29; H, 3.42; N, 9.52;
3 2 2
Synthesis of compounds 2 and 3 (general procedure).46 A mix-
S, 14.52. H NMR (CDCl ), δ: 6.60 (s, 1 H, Pyrim); 6.65 (d, 2 H,
1
3
ture of phthalic or naphthalic anhydride (7.3 mmol) and
-amino-4,6-dimethylpyrimidine (8.1 mmol, 1 g) in dry DMF
10 mL) was refluxed under an argon atmosphere for 24 h until
an orange-brown suspension formed. Then excess DMF was
distilled off under reduced pressure. The residue was washed with
hexane and dried in air. The product was purified by recrystal-
lization from an appropriate solvent.
2 CH=, J = 15.8 Hz); 7.09 (d, 2 H, Th, J = 5.0 Hz); 7.29 (d, 2 H,
Th, J = 2.5 Hz); 7.35 (d, 2 H, Th, J = 4.9 Hz); 7.40 (d, 2 H, PI,
J = 5.4 Hz); 7.44 (d, 2 H, PI, J = 5.1 Hz); 8.12 (d, 2 H, 2 CH=,
2
(
1
3
J = 15.5 Hz). C NMR (CDCl ), δ: 107.9, 125.6, 126.6, 127.5,
3
127.9, 128.8, 129.5, 133.3, 136.1, 139.2, 141.5, 163.6.
N-{4,6-Bis[(E)-2-(1-methyl-1H-pyrrol-2-yl)ethenyl]pyrim-
idin-2-yl}phthalimide (7). Red crystalline compound. Yield
30 mg (72%), m.p. 195 C. Found (%): C, 71.40; H, 4.59; N, 15.71.
N-(4,6-Dimethylpyrimidin-2-yl)phthalimide (2). Yellow crys-
talline compound. Yield 3.2 g (80%), m.p. 118—120 C. Found (%):
C
26H21N O . Calculated (%): C, 71.71; H, 4.86; N, 16.08.
5 2
1
C, 66.51; H, 4.41; N, 16.04. C14H11N O . Calculated (%):
H NMR (CDCl ), δ: 3.89 (s, 6 H, 2 N—CH ); 6.28 (q, 2 H,
3
2
3
3
–
1
C, 66.40; H, 4.38; N, 16.59. IR (Nujol mulls), /cm : 3366,
Pyr, J = 3.8 Hz); 6.32 (s, 1 H, Pyrim); 6.44 (d, 2 H, 2 CH=,
J = 15.5 Hz); 6.88 —6.91 (m, 4 H, Pyr); 7.80 (m, 4 H, PI); 8.45
1
1
2
673, 1608, 1580, 1266. H NMR (CDCl ), δ: 2.57 (s, 6 H,
3
1
3
CH ); 7.12 (s, 1 H, Pyrim); 7.79 q, 2 H, PI, J = 7.8 Hz); 7.93
(d, 2 H, 2 CH=, J = 15.4 Hz). C NMR (CDCl ), δ: 34.3, 68.2,
3
3
1
3
(
q, 2 H, PI, J = 7.9 Hz). C NMR (CDCl ), δ: 23.6, 119.6,
107.9, 108.2, 108.6, 109.0, 109.1, 109.7, 109.9, 112.4, 125.1,
125.4, 125.6, 128.8, 130.8, 131.1.
3
1
23.7, 131.6, 134.3, 152.7, 165.9, 169.2.
N-(4,6-Dimethylpyrimidin-2-yl)-1,8-naphthalimide (3). Yellow
N-{4,6-Bis[(E)-2-(4-methylphenyl)ethenyl]pyrimidin-2-yl}-
1,8-naphthalimide (8). Yellow crystalline compound. Yield 40 mg
(83%), m.p. 109 C. Found (%): C, 80.05; H, 4.84; N, 7.76.
crystalline compound. Yield 4.1 g (85%), m.p. 253—255 C.
Found (%): C, 70.97; H, 4.20; N, 13.18. C H N O . Calculat-
1
8
13
3
2
–
1
1
ed (%): C, 71.28; H, 4.32; N, 13.85. IR (Nujol mulls), /cm
:
C H N O . Calculated (%): C, 80.45; H, 4.96; N, 8.28. H NMR
34
25
3 2
1
3
335, 1774, 1705, 1670, 1584, 1246. H NMR (CDCl ), δ: 2.59
(CDCl ), δ: 2.37 (s, 6 H, 2 CH ); 6.71 (s, 1 H, Pyrim); 6.87
3
3
3
(
s, 6 H, 2 CH ); 7.15 (s, 1 H, Pyrim); 7.74 (t, 2 H, NPI, J = 7.8 Hz);
(d, 2 H, 2 CH=, J = 16.0 Hz); 7.18 (d, 4 H, C H , J = 7.8 Hz); 7.48
6 4
3
8
.23 (d, 2 H, NPI, J = 8.1 Hz); 8.59 (d, 2 H, NPI, J = 7.1 Hz).
(d, 4 H, C H , J = 7.9 Hz); 7.75 (t, 2 H, NPI, J = 7.4 Hz,
6
4
1
1
3
C NMR (CDCl ), δ: 23.8, 120.2, 122.7, 126.9, 127.4, 128.7,
J2 = 8.1 Hz); 7.89 (d, 2 H, 2 CH=, J = 16.0 Hz); 8.3 (dd, 2 H,
3
1
31.4, 131.8, 133.3, 134.5, 135.3, 156.1, 163.9, 169.8.
NPI, J = 8.3 Hz, J = 8.4 Hz); 8.61 (dd, 2 H, NPI, J = 7.4 Hz,
1
2
1
1
3
Synthesis of compounds 4—11 (general procedure). A mixture
J2 = 7.3 Hz). C NMR (CDCl ), δ: 21.4, 107.3, 120.1, 122.9,
3
of 4,6-dimethyl-2-substituted pyrimidine 2 or 3 (0.1 mmol) and
appropriate carbaldehyde (0.2 mmol) was refluxed for 5 h under
an argon atmosphere in a 5 M aqueous NaOH solution in the
presence of a catalytic amount of Aliquat 336. Then the solution
was cooled to ~20 C, poured into water, and extracted with
126.6, 126.9, 128.0, 129.7, 131.4, 132.8, 134.4, 139.1, 156.1,
140.3, 163.9, 168.9.
N-{4,6-Bis[(E)-2-(9-hexyl-9H-carbazol-3-yl)ethenyl]pyrim-
idin-2-yl}-1,8-naphthalimide (9). Red crystalline compound.
Yield 60 mg (73%), m.p. (decomp.) ~ 200 C. Found (%):
CH Cl . The combined organic extracts were washed with water
C, 81.12; H, 6.25; N, 7.86. C56H51N O . Calculated (%):
2
2
5 2
1
and dried over Na SO . Excess solvent was distilled off, and the
C, 81.42; H, 6.22; N, 8.48. H NMR (CDCl ), δ: 0.86 (t, 6 H,
3
2
4
residue was dried in air. Compounds 4—11 were isolated and
2 NCH CH CH CH CH CH , J = 7.0 Hz); 1.39—1.28 (m, 12 H,
2 2 2 2 2 3
purified by silica gel column chromatography (CH Cl ).
2 NCH CH CH CH CH CH ); 1.87 (m, 4 H, 2 NCH CH -
2
2
2
2
2
2
2
3
2
2
N-{4,6-Bis[(E)-2-(4-methylphenyl)ethenyl]pyrimidin-2-yl}-
phthalimide (4). Yellow crystalline compound. Yield 40 mg (85%),
CH CH CH CH ); 4.27 (t, 4 H, 2 N—CH , J = 7.1 Hz); 6.76
2 2 2 3 2
(s, 1 H, Pyrim); 6.93 (d, 2 H, 2 CH=, J = 15.9 Hz); 7.26—7.48
(m, 10 H, Cz); 7.74 (t, 2 H, NPI, J = 7.5 Hz); 8.10—8.17 (m, 4 H,
2 CH=, NPI); 8.22 (d, 2 H, NPI, J = 8.3 Hz); 8.31 (s, 2 H, Cz);
m.p. 132.5 C. Found (%): C, 78.31; H, 4.94; N, 8.63. C H N O .
3
0
23
3 2
1
Calculated (%): C, 78.75; H, 5.07; N, 9.18. H NMR (CDCl ),
3
1
3
δ: 2.41 (s, 6 H, 2 CH ); 6.76 (s, 1 H, Pyrim); 6.93 (d, 2 H,
8.60 (d, 2 H, NPI, J = 7.3 Hz). C NMR (CDCl ), δ: 13.4,
3
3
2
CH=, J = 15.9 Hz); 7.23 (d, 4 H, C H , J = 8.0 Hz); 7.61—7.44
22.5, 26.9, 28.9, 31.5, 43.4, 106.8, 107.2, 108.9, 109.1, 109.2,
119.6, 120.6, 121.0, 122.8, 123.0, 123.6, 125.9, 126.3, 126.6,
126.9, 127.5, 131.4, 134.4, 136.9, 141.1, 141.7, 168.5.
6
4
1
3
(
(
m, 8 H, C H , PI); 7.83 (d, 2 H, 2 CH=, J = 16.0 Hz). C NMR
6 4
CDCl ), δ: 21.3, 107.4, 109.0, 125.5, 127.6, 129.6, 133.3, 136.8,
3
1
39.5, 163.2, 164.1, 169.2 (overlapping of signals).
N-{4,6-Bis[(E)-2-(thiophen-2-yl)ethenyl]pyrimidin-2-yl}-
1,8-naphthalimide (10). Yellow crystalline compound. Yield 30 mg
(68%), m.p. 193 C. Found (%): C, 68.24; H, 3.37; N, 7.98;
N-{4,6-Bis[(E)-2-(9-hexyl-9H-carbazol-3-yl)ethenyl]pyr-
imidin-2-yl}phthalimide (5). Red crystalline compound. Yield 60
mg (79%), m.p. 80.6 C. Found (%): C, 80.01; H, 6.24; N, 8.66.
S, 12.57. C28H17N O S . Calculated (%): C, 68.41; H, 3.49;
3 2 2
1
1
C H N O . Calculated (%): C, 80.49; H, 6.36; N, 9.03. H NMR
N, 8.55; S, 13.05. H NMR (CDCl ), δ: 6.65 (s, 1 H, Pyrim);
5
2
49
5
2
3
(
CDCl ), δ: 0.86 (t, 6 H, 2 NCH CH CH CH CH CH ,
6.77 (d, 2 H, 2 CH=, J = 15.6 Hz); 7.06 (d, 2 H, Th, J = 3.6 Hz);
7.23 (d, 2 H, Th, J = 3.5 Hz); 7.32 (d, 2 H, Th, J = 5.0 Hz); 7.53
(d, 2 H, NPI, J = 5.6 Hz); 7.73 (dd, 4 H, NPI, J = 5.6 Hz); 7.92
3
2
2
2
2
2
3
J = 7.0 Hz); 1.39—1.28 (m, 12 H, 2 NCH CH CH CH CH CH );
2
2
2
2
2
3
1
2
.87 (m, 4 H, 2 NCH CH CH CH CH CH ); 4.28 (t, 4 H,
2 2 2 2 2 3
1
3
N—CH , J = 7.3 Hz); 6.74 (s, 1 H, Pyrim); 6.91 (d, 2 H, 2 CH=,
(d, 2 H, 2 CH=, J = 15.6 Hz). C NMR (CDCl ), δ: 108.0,
2
3
J = 15.8 Hz); 7.29—7.26 (m, 6 H, Cz); 7.40 (d, 4 H, Cz, J = 8.3 Hz);
.48 (t, 2 H, Cz, J = 7.9 Hz, J = 7.3 Hz); 7.77 (d, 2 H, PI,
125.6, 126.7, 127.9, 128.8, 129.0, 130.8, 132.6, 141.6, 163.0,
163.7, 167.6 (overlapping of signals).
7
1
2

New polycyclic aromatic imides
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 9, September, 2019
1713
N-{4,6-Bis[(E)-2-(1-methyl-1H-pyrrol-2-yl)ethenyl]pyrim-
idin-2-yl}-1,8-naphthalimide (11). Red crystalline compound.
Yield 30 mg (69%), m.p. (decomp.) ~187 C. Found (%): C, 74.30;
20. F.-P. Wu, H. Un, Y. Li, H. Hu, Y. Yuan, B. Yang, K. Xiao,
W. Chen, J.-Y. Wang, Z.-Q. Jiang, J. Pei, L.-S. Liao, Chem.
Eur. J., 2017, 23, 14723.
H, 4.60; N, 13.84. C H N O . Calculated (%): C, 74.21; H, 4.77;
21. S. Ge, B. Li, X. Meng, H. Yan, M. Yang, B. Dong, Y. Lu,
Dyes Pigm., 2018, 148, 147.
3
0
23
5 2
1
N, 14.42. H NMR (CDCl ), δ: 3.77 (s, 6 H, 2 N—CH ); 6.18
3
3
(
m, 2 H, Pyr); 6.45 (s, 1 H, Pyrim); 6.56—6.73 (m, 6 H, Pyr, 2 CH=);
22. J.-Z. Liao, X.-Y. Wu, J.-P. Yong, H.-L. Zhang, W.-B. Yang,
R. Yu, C.-Z. Lu, Cryst. Growth Des., 2015, 15, 4952.
23. W. Zhu, M. Hu, R. Yao, H. Tian, J. Photochem. Photobiol.
A, 2003, 154, 169.
7
.50 (m, 2 H, NPI); 7.68 (m, 2 H, NPI); 7.86 (d, 2 H, 2 CH=,
1
3
J = 15.8 Hz); 8.57 (d, 2 H, NPI, J = 7.3 Hz). C NMR (CDCl ),
3
δ: 34.4, 68.2, 107.6, 109.6, 121.8, 122.7, 125.6, 127.4, 128.8,
1
30.8, 132.6, 156.6, 164.5, 170.1 (overlapping of signals).
24. H. Cao, V. Chang, R. Hernandez, M. D. Heagy, J. Org. Chem.,
2
005, 70, 4929.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 18-33-00323
mol_a).
25. M. Li, Y. Liu, R. Duan, X. Wei, Y. Yi, Y. Wang, C.-F. Chen,
Angew. Chem., Int. Ed. Engl., 2017, 56, 8818.
2
2
6. H. Yan, X. Meng, B. Li, S. Ge, Y. Lu, J. Mater. Chem. C,
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017, 5, 10589.
7. M. Daskeviciene, S. Urnikaite, G. Planciunaite, T. Malinauskas,
A. Gruodis, M. Viliunas, E. Kamarauskas, V. Gaidelis,
V. Jankauskas, V. Getautis, Dyes Pigm., 2018, 158, 157.
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Received March 26, 2019;
in revised form May 28, 2019;
accepted June 20, 2019
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