Synthesis and optical properties of new 2-oxo-4-vinyl-2H-chromene-3-carbonitrile dyes

Article abstract of DOI:10.1016/j.mencom.2019.05.020

New derivatives of 2-oxo-4-vinyl-2H-chromene-3-carbonitrile have been synthesized by the Knoevenagel reaction of 4-methyl-2-oxo-2H-chromene-3-carbonitrile with aromatic and heteroaromatic aldehydes. The first hyperpolarizability β for the obtained compoun

Full text of DOI:10.1016/j.mencom.2019.05.020

Mendeleev
Communications
Mendeleev Commun., 2019, 29, 301–303
Synthesis and optical properties of new
2-oxo-4-vinyl-2H-chromene-3-carbonitrile dyes
a
a
a
Konstantin S. Levchenko,* Konstantin A. Chudov, Evgeni V. Zinoviev,
b,c
d
a
Konstantin A. Lyssenko, Artem N. Fakhrutdinov, Dmitri U. Demin,
a
e
a
a
Nikolay O. Poroshin, Anna A. Zhukova, Pavel S. Shmelin and Evgeni P. Grebennikov
a
Central Research Institute of Technology ‘Tekhnomash ,’ 121108 Moscow, Russian Federation.
E-mail: k.s.levchenko@gmail.com
Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation
G. V. Plekhanov Russian University of Economics, 117997 Moscow, Russian Federation
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian
Federation
b
c
d
e
I. M. Sechenov First Moscow State Medical University, 119991 Moscow, Russian Federation
DOI: 10.1016/j.mencom.2019.05.020
Me
O
New derivatives of 2-oxo-4-vinyl-2H-chromene-3-carbonitrile
have been synthesized by the Knoevenagel reaction of
S
N
0
0
.04
.03
R =
R =
R =
NEt2
Me
N
4
-methyl-2-oxo-2H-chromene-3-carbonitrile with aromatic
O
N
and heteroaromatic aldehydes. The first hyperpolarizability
b for the obtained compounds was calculated using M05-2X
functional and 6-31+G(d) basis set; their optical properties
and solvatochromism in solvents of various polarity were
examined. The crystal structure for one representative of the
synthesized compounds was determined by XRD.
R
NPh2
R =
Me
Me
Me
0.02
O
R
MeO
0
.01
R =
N
NEt2
0.00
2
90 340 390 440 490 540 590 640 690 740
O
O
l/nm
In the last decades the development of organic nonlinear optical
of solid state lasers19,20 as well as dye sensitizers for solar
2
1,22
(NLO) materials has attracted much attention due to their potential
cells having high photovoltage.
However, there are only few
application in information processing, fiber communication,
optical switching and information storage.1 The increasing
amount of transmitted data requires the use of high-speed electro-
optical modulators operating at a frequency above 100 GHz,
which can be achieved with the NLO materials only. Compared
to the well-known inorganic NLO crystals, such as lithium
niobate, KH PO or TeO , the organic NLO materials are charac-
investigations of dyes with a 3-cyano-2-oxo-2H-chromen-4-yl
moiety as an acceptor part.
–7
Here, the synthesis and the optical properties of new
chromophores containing the 3-cyano-2-oxo-2H-chromen-4-yl
acceptor are described. The synthesis was carried out starting
from 4-methyl-2-oxo-2H-chromene-3-carbonitrile 1 obtained
2
3,24
according to the known method
by heating ethyl cyano-
2
4
2
terized with less response time, wider bandwidth, higher electro-
optic coefficient and better processability.
acetate, ammonium acetate and o-hydroxyacetophenone at 220°C
for 15 min (Scheme 1). The introduction of the donor fragments
into 4-position of compound 1 was realized by the Knoevenagel
1,8
The organic NLO materials are based on donor–acceptor
chromophores D–p–A, where the donor and acceptor moieties
are connected through conjugated bonds. Diethylaniline and
julolidine derivatives are commonly used as the donor parts.
Olefinic polyene-type structures and heteroaromatic compounds
with low aromatization energy, utilized as the p-bridges between the
donor and the acceptor parts, provide an effective charge transfer.
The most commonly used acceptors are malononitrile derivatives,
such as 5,5-disubstituted 3-cyano-2-dicyanomethylidene-5H-
†
reaction with corresponding aldehydes. Aldehydes 2a–c are
2
5
commercially available or can be easily obtained. Aldehydes
2d and 2e were synthesized by known procedures.2
5,26
The
reactions were carried out in acetonitrile or ethanol medium in
the presence of l-proline or piperidine as a catalyst with similar
results. Acetic anhydride was also tested as a solvent and a
dehydrating agent. We have found that acetonitrile is the most
suitable solvent due to negligible amount of by-products, although
the total yields are comparable when using ethanol or acetic
anhydride.
9
,10
furan-4-yl,
3-cyano-2-dicyanomethylidene-5-oxo-1H-pyrrol-
1
1,12
13
4-yl
and 1,3-bis(dicyanomethylene)-1H-inden-2-yl derivatives,
etc. There are as well several examples of using benzopyran-type
moieties, namely 4-dicyanomethylidene-4H-chromen-2-yl, as an
acceptor in push–pull chromophores.14
†
General procedure for the synthesis of compounds 3a–e. To a solution
of 4-methyl-2-oxo-2H-chromene-3-carbonitrile 1 (185 mg, 1 mmol)
and aldehyde 2a–e (1 mmol) in acetonitrile (5 ml) one drop of piperidine
was added. The reaction mixture was stirred under reflux for appropriate
time (see Scheme 1). The precipitate formed was filtered off, washed with
ethanol and dried in air. If no solid precipitate formed, the solvent was
distilled off in vacuo. The residue was purified by crystallization or by
column chromatography.
Previously we demonstrated the use of 3-cyano-2-oxo-2H-
chromen-4-yl part as an acceptor as well as its application as a
cheap raw material for the synthesis of donor–acceptor chromo-
1
5,16
phores.
2
-Oxo-2H-chromenes are well-known as donor parts of
17,18
fluorescent dyes,
light-stable dyes as fluorescent components
©
2019 Mendeleev Communications. Published by ELSEVIER B.V.
–
301 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2019, 29, 301–303
Table 1 The absorption data for the synthesized products 3a–e in various solvents.
lmax/nm
Dlmax/nma
e /dm mol cm–1
b
3
–1
b (a.u.)c
Compound
1
,4-dioxane
PhCl
36.8
CH Cl
Me CO
MeCN
45.6
EtOH
51.9
2
2
2
ET(30)d
36
40.7
42.2
–
–
–
3
3
3
3
3
a
b
c
d
e
466
486
518
506
529
488
508
549
534
560
490
518
560
540
560
468
501
548
524
535
470
506
545
527
574
489
523
568
548
559
24
37
50
42
45
15660
9261
5792
15140
15698
19303.3
15598.9
15097.7
8434.2
54453.0
a
b
c
Dlmax is the maximum difference between absorption maxima in different solvents. e is the molar extinction calculated for 1,4-dioxane solution. b is the
d
–1 27
first hyperpolarizability. E (30) is the empirical parameter of solvent polarity (kcal mol ).
T
compounds 3a, 3b and 3d. Interestingly, the absorption maximum
R
in acetonitrile for compound 3e is in a longer wavelength range,
compared with the absorption maximum in ethanol, which is
accounted for by the formation of specific solvate forms.
Me
N
N
R
i
+
The structure of compound 3e was confirmed by XRD
‡
O
(
Figure 2). It crystallizes as solvate with chloroform in the
O
O
O
O
centrosymmetric space group P2 /n. The molecule 3e is almost
1
2a–e
3a–e
1
planar with maximum deviation from planarity due to rotation
around the C(3)–C(11) bond, with torsion angle C(2)–C(3)–
C(11)–C(12) being 18.7°. In the crystal, the cyano group of
compound 3e participates in the shortened N···Cl interactions
with the chloroform molecule: N–Cl distance is 2.99–3.07 Å
and N–Cl–C angle is 159–167°, which can be considered as the
halogen bond. In addition, the molecules participate in a strong
stacking interaction between the 2-oxo-2H-chromene-3-carbo-
nitrile rings, with the shortest C···C contact being 3.37 Å.
Considering the pronounced solvatochromism of compounds
a R =
d R =
b R =
c R =
NPh2
Me
NEt2
N
S
e R =
Me
Me
Me
N
MeO
NEt2
3
Reaction time/h Yield (%)
3
a–e, it is reasonable to suppose that these molecules can be
a
b
c
d
e
23
24
24
48
21
47
50
38
39
30
characterized by high values of first hyperpolarizability b for the
thermal ellipsoids at p = 50%. For all the molecules we performed
the geometry optimization without symmetry restriction using
the density functional theory with PBE0 approximation and
def-2-TZVP basis set. The calculations of b were carried out
Scheme 1 Reagents and conditions: i, MeCN, piperidine, reflux.
All products were characterized by H and 13C NMR as well
as HRMS methods. Optical properties of compounds 3a–e are
summarized in Figure 1 and Table 1.
1
C(8)
C(7)
C(6)
C(9)
C(5)
C(26)
C(4)
O(1)
C(1)
With the solvents varying from slightly polar 1,4-dioxane to
moderately polar dichloromethane, a shift of 24–42 nm of the
absorption maxima to longer wavelength has been observed for
all the chromophores 3a–e.
In a series from weakly or moderately polar solvents to highly
polar ones, a negative solvatochromism was observed. With
increasing polarity in a group of highly polar solvents, namely
acetone, acetonitrile and ethanol, a linear relationship occurs for
C(21)
C(25)
C(20)
C(19)
N(2)
C(27)
S(1)
C(11)
C(12)
C(3)
C(22)
C(18)
C(16)
C(2)
O(2)
C(24)
C(10)
N(1)
C(28)
C(23)
C(13)
C(17)
C(15)
Cl(2)
C(14)
Cl(1) C(1S)
Cl(3)
0
0
0
.04
.03
.02
.01
Figure 2 Molecular structure of compound 3e.
Crystal data for 3e. C H Cl N O S, monoclinic, space group P2 /n,
3
3
3
3
3
a
b
c
‡
29 25
3
2
2
1
at 120(2) K: a = 9.511(3), b = 7.209(2) and c = 39.548(12) Å, b =
3
–3
=
90.018(6)°, V = 2711.8(15) Å , Z = 4, Z' = 1, d = 1.401 g cm .
d
e
calc
Intensities of 30208 reflections were measured using Bruker APEX-II
CCD [l(MoKa) = 0.71072 Å], 2q < 55° and 6252 independent reflections
were used in the further refinement. The structure was solved by direct
2
0
0
method and refined by the full-matrix least-squares technique against F
in the anisotropic–isotropic approximation. The refinement converged to
wR = 0.1755 and GOF = 0.877 for all independent reflections [R = 0.0691
2
1
.00
2
was calculated against F for 2507 observed reflections with I > 2s(I)].
All calculations were performed using SHELXTL-2014/6.
CCDC 1874236 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk.
90 340 390 440 490 540 590 640 690 740
l/nm
Figure 1 The absorption spectra of the synthesized products 3a–e, C =
0.003 mg ml .
–
1
=
–
302 –

Mendeleev Commun., 2019, 29, 301–303
using M05-2X/6-31+G(d) approximation that had been shown to
8 Y. Shi, D. Frattarelli, N. Watanabe, A. Facchetti, E. Cariati, S. Righetto,
E. Tordin, C. Zuccaccia, A. Macchioni, S. L. Wegener, C. L. Stern,
M. A. Ratner and T. J. Marks, J. Am. Chem. Soc., 2015, 137, 12521.
be the appropriate method.2
8–31
The b values were calculated by the numerical second derivative
of electric dipole moment with respect to the applied field, as
implemented into the Gaussian 09 program. For all molecules
9
D. Briers, L. De Cremer, G. Koeckelberghs, S. Foerier, T. Verbiest and
C. Samyn, Macromol. Rapid Commun., 2007, 28, 942.
1
0 Y. V. Pereverzev, K. N. Gunnerson, O. V. Prezhdo, P. A. Sullivan,
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3
a–e, the nature of the emission band was estimated by means
of TD-DFT calculation with application of the conductor-like
32
polarization continuum model CPCM of acetonitrile solvent.
The TD-DFT calculations have revealed that the lowest energy
transitions S1®S0 are mainly HOMO to LUMO, which cor-
responds to the transition from the donor part, designated as R in
Scheme 1, to the acceptor one, namely the 2-oxo-2H-chromene-
1
1
1
3
-carbonitrile ring. The b values are significantly higher than
15 K. A. Chudov, K. S. Levchenko, N. O. Poroshin, E. V. Zinoviev, G. E.
Adamov, P. S. Shmelin and E. P. Grebennikov, XII Russian Conference
‘Technologies and Materials for Extreme Conditions (Laser Technologies,
Electric Current Sources and Materials)’, Tuapse, 2017, p. 227.
those for the family of stilbene derivatives or their thiophene
analogues.
3
3–35
Compound 3e has the highest b value equal to
5
4453.0 a.u., which is only slightly lower that for 2-dicyano-
1
6 K. S. Levchenko, K. A. Chudov, N. O. Poroshin, E. V. Zinoviev,
P. A. Chicheva, E. A. Shohina, P. S. Shmelin and E. P. Grebennikov,
VII International Conference on Photonics and Information Optics,
Moscow, 2018, p. 138.
methylidene-3-cyano-4-{2E-[2-(2E-{4-[di(2-acetoxyethyl)-
amino]phenyl}vinyl)-3,4-dibutylthien-5-yl]vinyl}-5,5-dimethyl-
2
synthesized compounds can be promising for the design of NLO
materials.
,5-dihydrofuran (FTC).3
6,37
Thus, we can propose that the
1
1
1
7 A. Y. Bochkov, I. O. Akchurin, O. A. Dyachenko and V. F. Traven,
Chem. Commun., 2013, 49, 11653.
8 I. O. Akchurin, A. I. Yakhutina, A. Y. Bochkov, N. P. Solovjova,
M. G. Medvedev and V. F. Traven, J. Mol. Struct., 2018, 1160, 215.
9 A. Sharma, International Journal of Environmental Science: Development
and Monitoring (IJESDM), 2013, 4, special issue 3, 12.
In summary, a series of new 2-oxo-4-vinyl-2H-chromene-
3-carbonitrile derivatives were synthesized by the Knoevenagel
reaction of 4-methyl-2-oxo-2H-chromene-3-carbonitrile with
aromatic and heteroaromatic aldehydes. The first hyperpolari-
zability b of the obtained compounds was calculated using M05-2X
functional and 6-31+G(d) basis set. Optical properties and solvato-
chromism in solvents of various polarity, namely 1,4-dioxane,
chlorobenzene, dichloromethane, acetonitrile and ethanol, were
explored. The new class of dyes may be useful for NLO devices
and other applications.
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This work was supported by the Russian Science Foundation
project no. 17-73-10433). The X-ray diffraction data were obtained
using the equipment of Center for Molecules Composition
Studies of INEOS, RAS. DFT calculations were supported by the
Russian Foundation for Basic Research (grant no. 18-33-20075).
(
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1
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2019.05.020.
1
0
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Received: 10th December 2018; Com. 18/5767
–
303 –