Electron-Withdrawing Substituted Quinazoline Push-Pull Chromophores: Synthesis, Electrochemical, Photophysical and Second-Order Nonlinear Optical Properties

Article abstract of DOI:10.1002/ejoc.202000870

A series of chromophores bearing 4-cyanoquinazoline, 2-(4-cyanophenyl)quinazoline or 2-(4-trifluorophenyl)quinazoline electron–acceptor (A) and 5-(4-aminophenyl)thiophen-2-yl or 4-aminophenyl electron-donor (D) units has been designed. The influence of the electron-withdrawing substituent on the pyrimidine core as well as the nature of the amino electron donating group has been studied by cyclic voltammetry, UV/Vis and emission spectroscopy. Whereas 2-(4-cyanophenyl)quinazoline and 2-(4-trifluorophenyl)quinazoline derivatives are highly luminescent in chloroform solution, 4-cyanoquinazolines are poorly emissive. Interestingly all compounds are luminescent in the solid state with the emission ranging from blue to red. The second order nonlinear optical properties were studied using electric field induced second harmonic generation (EFISH) method. Quantum-chemical calculations corroborate the aforementioned experimental results.

Full text of DOI:10.1002/ejoc.202000870

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Electron-withdrawing substituted quinazoline push-pull
chromophores: Synthesis, electrochemical, photophysical and
second order nonlinear optical properties
Authors: Tatiana N. Moshkina, Pascal Le Poul, Alberto Barsella,
Oldřich Pytela, Filip Bureš, Françoise Robin-Le Guen, Sylvain
Achelle, Emiliya V. Nosova, Galina N. Lipunova, and Valery
N. Charushin
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to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202000870
Link to VoR: https://doi.org/10.1002/ejoc.202000870
01/2020

10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
Electron-withdrawing substituted quinazoline push-pull
chromophores: Synthesis, electrochemical, photophysical
and second order nonlinear optical properties
Tatiana N. Moshkina,[a] ,[b] Pascal Le Poul,[a] Alberto Barsella [c]
,
Oldřich Pytela
, ,
[d] Filip Bureš [d]
Françoise Robin-Le Guen,[a] Sylvain Achelle
Valery N. Charushin[b], [e]
,
*[a] Emiliya V. Nosova [b], [e] Galina N. Lipunova [e]
,
*
,
and
[a]
T.N. Moshkina, Dr. P. Le Poul, Prof. F. Robin-Le Guen, Dr. S. Achelle
Univ. Rennes, CNRS, Institut des Sciences Chimiques de Rennes - UMR 6226, F 35000 Rennes, France.
https://iscr.univ-rennes1.fr/sylvain-achelle
E-mail: sylvain.achelle@univ-rennes1.fr
[b]
T.N. Moshkina, Prof. E.V. Nosova, Prof. V.N. Charushin
Department of Organic and Biomolecular Chemistry
Ural Federal University
19 Mira Str., Yekaterinburg 620002, Russian Federation
E-mail: emilia.nosova@yandex.ru
[c]
[d]
[e]
Dr. A. Barsella
Département d'Optique Ultrarapide et Nanophotonique, IPCMS, UMR CNRS 7504, Université de Strasbourg,
23 rue de Loess, BP 43 67034 Strasbourg Cedex 2, France
Prof. O. Pytela, Prof. F. Bureš
Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice,
Studenská 573, Pardubice 53210, Czech Republic
Prof. E.V. Nosova, Prof. G.N. Lipunova, Prof. V.N. Charushin
I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
620219 Yekaterinburg, Russian Federation
Supporting information for this article is given via a link at the end of the document.
Abstract: A series of chromophores bearing 4-cyanoquinazoline, 2-
such as second order NLO phenomena and two-photon
absorption (TPA). The second order NLO properties have found
applications as second harmonic generation, used for example
to obtain green laser from an infrared source at 1064 nm,[7]
second harmonic microscopy[8] and terahertz generation.[9] NLO
(4-cyanophenyl)quinazoline
or
2-(4-trifluorophenyl)quinazoline
electron-acceptor (A) and 5-(4-aminophenyl)thiophen-2-yl or 4-
aminophenyl electron-donor (D) units has been designed. The
influence of the electron-withdrawing substituent on the pyrimidine
core as well as the nature of the amino electron donating group has
been studied by cyclic voltammetry, UV-Vis and emission
spectroscopy. Whereas 2-(4-cyanophenyl)quinazoline and 2-(4-
trifluorophenyl)quinazoline derivatives are highly luminescent in
chloroform solution, 4-cyanoquinazolines are poorly emissive.
Interestingly all compounds are luminescent in the solid state with
the emission ranging from blue to red. The second order nonlinear
optical properties were studied using electric field induced second
response is directly related to the ICT and can be easily tuned
[1,2,11]
by varying the D/A couple,[1,10] the π-conjugated spacer
or
by branching the chromophore to adopt quadrupolar or octupolar
structure.[12]
The pyrimidinyl (1,3-diazinyl) fragment has been widely used
as electron-deficient part in push-pull structures.[13] The
luminescence properties of pyrimidine fluorophores are highly
sensible to external stimuli and have been used as sensors of
polarity,[14] pH,[14b,c] metal cations[15] and nitrogen explosives.[16]
Push-pull pyrimidine derivatives are also well-known for their
TPA properties.[17] Some of us have studied the second order
NLO properties of pyrimidine chromophores: even if the NLO
responses of styrylpyrimidine derivatives remain moderate,[18]
extension of the π-conjugated spacer,[19] incorporation of a metal
centre between the D/A parts,[20] and reinforcement of the
electron-withdrawing character of pyrimidinyl fragment by N-
complexation or N-methylation[21] induce a significant increase of
the second order hyperpolarizability tensor. Akdas-Kilig and co-
workers have also described octopolar structures based on
bipyrimidinyl electron withdrawing central part.[22] On the
contrary, quinazoline (benzopyrimidine) chromophores have
been studied only recently.[13a,b,23] Some of these compounds
exhibit strong luminescence properties.[24] The quinazolinyl
moiety can be considered as stronger electron-withdrawing part
than the corresponding pyrimidinyl group due to the possibility of
extra electron delocalization into the fused benzene ring.
Stronger ICT in quinazoline chromophores is illustrated by red-
harmonic
generation
(EFISH) method. Quantum-chemical
calculations corroborate the aforementioned experimental results.
Introduction
Over the last 25 years, there has been a considerable
interest in the design of organic push-pull chromophores having
electron-donating group (D) linked to an electron-withdrawing
one (A) via a π-conjugated bridge (D-π-A structure).[1] In these
compounds, intramolecular charge transfer (ICT) occurs and
generation of new low-energy molecular orbital induces unique
optical and electrochemical properties.[2] These chromophores
have found key applications as fluorescent sensors,[3] in
optoelectronic, particularly for photovoltaics,[4] organic field effect
transistor (OFETs)[5] and in organic light emitting diodes
(OLEDs).[6] The generation of a molecular dipole in push-pull
chromophores induces also nonlinear optical (NLO) properties
1
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10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
shifted absorption and emission with regards to their pyrimidine
analogues.[13b,24c] To the best of our knowledge, quinazoline
chromophores have not been studied for their NLO properties so
far, and, therefore, we report herein designed of a series of
quinazoline push-pull chromophores 1-3 (Figure 1). In these
structures, the electron-withdrawing character of the quinazoline
ring is reinforced by cyano and trifluoromethyl substituents.
Electrochemical, linear and nonlinear optical properties of these
compounds were carefully studied experimentally and
theoretically using DFT calculations. The influence of the
cyanophenyl- and trifluoromethylphenyl- branches was
determined by comparison with already known compound A.[24c]
O
N
NH2
O
H
6a (77%)
or
O
R
CN
CuCl2, EtOH
5a,b
EtOH
NH2
O
NH2
NH
4
N
H
CF3
6b (71%)
R'
N
O
N
B
N
N
POB 3, NEt3
toluene
,
i o ii
NH
80 o
C
N
(60-78%)
R
7a,b
R
8a,b (40-85%)
1a-c, 2a-c
R = CN (5a, 7a, 8a), CF3 (5b, 7b, 8b)
R
1a: R = CN, R' = NEt2 (69%)
1b: R = CN, R' = NPh2 (74%)
1c: R = CN, R' = ca bazol-9-yl (84%)
2a: R = CF3, R' = NMe2 (77%)
2b: R = CF3, R' = NPh2 (85%)
2c: R = CF3, R' = ca bazol-9-yl (39%)
Scheme 1. Synthesis of compounds 1 and 2. Reagents and conditions: (i)
Arylboronic acid or arylboronic acid pinacol ester (for 1c), PdCl2(PPh3)2, PPh3,
K2CO3, toluene, EtOH, 85 °C, Argon (for 1); (ii) Arylboronic acid, Pd(PPh3)4,
Na2CO3, toluene, EtOH, refluxing, N2 (for 2).
Both quinazolinones 7a,b were converted into 4-bromo
derivatives 8a,b by treatment with POBr3 in the presence of Et3N
in toluene. Further, bromo-derivative 8a subjected to the
PdCl2(PPh3)2-catalyzed Suzuki-Miyaura cross-coupling reaction
with arylboronic acid or 4-(9H-carbazol-9-yl)phenylboronic acid
pinacol ester to obtain the 4-cyanophenyl quinazolines 1.
Slightly different conditions were applied for the synthesis of
CF3-derivatives 2, namely, refluxing of bromo-quinazoline 8b
with arylboronic acid in the mixture of toluene and EtOH under
N2, using Pd(PPh3)4 as a catalyst and saturated solution of
Na2CO3 as a base.[24c] The quadruplet signals of CF3 group with
J = 272.1−272.9 Hz and carbon atoms (C3 and C5) of CF3-phenyl
fragment with J = 3.9 Hz in the 13C NMR of target quinazolines 2
were observed. In the mass spectra of quinazolines 1 the peak
of molecular ions with 47% (m/z 378 Da for compound 1a) and
with 100% (m/z 474 Da and m/z 472 Da for compound 1b,c,
respectively) relative intensity were registered.
Figure 1. Structures of quinazoline push-pull chromophores 1-3
Results and Discussion
Synthesis of dyes
The synthesis of the 2,4-disubstituted quinazolines 1 and 2
is summarized in Scheme 1. Compounds 8a,b were obtained in
three steps following the method similar to reported previously.
[25]
The condensation of anthranilamide
4
with 4-
cyanobenzaldehyde (5a) or 4-trifluoromethylbenzaldehyde (5b)
and subsequent oxidation with copper(II) chloride led to
quinazoline-3H-ones 7a,b. It is worth noting that the use of mild
conditions (stirring for 5 h at room temperature) gave Schiff base
6a as condensation product formed by 4-cyanobenzaldehyde 5a.
In the case of 4-trifluoromethylbenzaldehyde 5b and under the
same reaction conditions, the cyclization of Schiff base takes
place affording 2,3-dihydroquinazolin-4(1H)-one 6b. This fact
corresponds to the published results on interaction between
anthranilamides and benzaldehydes under various conditions
that reports 2,3-dihydroquinazolin-4(1H)-ones as thermodynamic
products.[26] 1H NMR spectroscopy of compound 6a
demonstrates signal of N=CH group at δ 8.69 ppm, whereas the
spectrum of 6b contains singlet of aliphatic CH atom at δ 5.86
that is in agreement with the proposed structures (see ESI,
Figures S1, S2).
The
synthetic
approach
to
2-[5-(4-
diethylaminophenyl)thiophen-2-yl]quinazoline derivative 3a has
been earlier developed in 56% yield.[27] It includes the
condensation
of
anthranilamide
with
(thiophen-2-
yl)carbaldehyde, chlorodesoxygenation, incorporation of cyano-
group at position 4 of quinazoline core, bromination with NBS
and subsequent palladium-catalyzed Suzuki-Miyaura cross-
coupling reaction. The new target chromophores 3b,c (Scheme
2) have been obtained using the same method. Purification by
column chromatography afforded 4-cyanoquinazoline 3b and 3c
in moderate yields. The structures of the compounds 3b,c were
confirmed by 1H and 13C NMR spectroscopy and mass
spectrometry. The peaks of the corresponding molecular ion
(m/z 480 and 478 Da, respectively) with 100% relative intensity
were observed in their mass spectra.
2
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10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
literature for carbazole and triphenylamine derivatives.[28] Finally,
except the chromophore 2a that exhibits an irreversible
reduction signal, a reduction process of compounds 1-3 is
reversible.
The HOMO/LUMO and electrochemical gap energies for
all compounds were calculated from the potentials values. When
employing the carbazol-9-yl donor (1c, 2c and 3c), the oxidation
is more difficult than in case of dialkylamino and diphenylamino
analogs, while the reduction changes to a lesser extent. In each
series, the highest electrochemical band gap is therefore
observed for carbazolyl derivatives. The dialkylamino derivatives
1a, 2a and 3a are easier to oxidize but more difficult to reduce
than their diphenylamino analogues 1b, 2b and 3b: the gap
values are therefore similar for both substituents in each series.
For a given donor substituent, when changing the acceptor
from CN to CF3 group, there is a small shift of the Ered values to
lower potential values (1 compared to 2), indicating a better
acceptor ability of the CN group. This electron-withdrawing effect
for both compounds 1b and 2b is confirmed by the
measurement of the reduction potential for their unsubstituted
analogue A (Ered= –3.34 V).
Scheme
2.
Synthesis
of
2-(5-(4-aminophenyl)thiophen-2-yl)-4-
cyanoquinazolines 3a-c. Reagents and conditions: (i) Arylboronic acid (for
3a,b) or arylboronic acid pinacol ester (for 3c), PdCl2(PPh3)2, PPh3, K2CO3,
toluene, EtOH, 85 °C, argon.
Electrochemical properties
Electrochemical behavior of compounds 1-3 were studied
by cyclic voltammetry in CH2Cl2 containing Bu4NPF6 electrolyte
at a scan rate of 0.1 V/s. The working electrode was a glassy
carbon disk; Pt wire was used as the counter electrode, and an
Ag wire as reference electrode. Ferrocene was used as internal
reference for electrochemical measurements. The first
oxidation/reduction peak potentials and their differences are
listed in Table 1; representative CV diagrams of compounds 1
and 3a are shown in Figure 2.
Finally, when the cyano group is on position 4 of the
quinazoline ring (compounds 3), the Ered values are less
negative than for compounds 1 and 2 pointing to a more
electron-withdrawing ability of this moiety. Compounds 3 are
also more easily reduced. This trend supports a stronger ICT for
these molecules compared to 1 and 2.
Table 1. Electrochemical data of compounds 1-3.
ox1
red1
∆E, V [b]
2.67
2.68
2.95
2.96
2.75
2.99
1.89
2.05
2.78
E1/2
,
E1/2
V [a]
,
EHOMO
,
ELUMO,
λmax
,
V [a]
eV [c]
eV [c]
Comp.
1a
nm [d]
464
0.553
–2.119
–2.053
–2.024
–2.372[e]
–2.129
–2.054
–1.581
–1.570
–1.863[e]
–5.33
–5.41
–5.71
–5.36
–5.40
–5.72
–5.09
–5.26
–5.70
–2.66
–2.73
–2.76
–2.40
–2.65
–2.73
–3.20
–3.21
–2.92
0.629
462
419
419
450
414
655
604
445
1b
0.922[e]
0.584
1c
2a
0.624
2b
0.606[e]
0.312
2c
3a
0.483
3b
0.553[e]
3c
red1
.
=1241/
Figure 2. Cyclic voltammograms of chromophores 1a (black), 1b (blue), 1c
(green) and 3a (red) in CH2Cl2 solutions with NBu4PF6 (0.1M) as the
electrolyte: first oxidation and reduction waves.
[a] All potentials are given versus ferrocene. [b] ∆E = E1/2ox1 – E1/2
[c] EHOMO/LUMO = – (Eox1/red1 + 4.8). [d] Calculated
[e] irreversible peaks Ep.
λ
max values (
λ
∆E).
Compounds 1-3 exhibit an oxidation process with the
potential ranging from 0.312 to 0.922 V vs ferrocene and a
reduction process from -1.570 to -2.372 V (Table 1), influenced
by the particular nature of the substituents. When the donor
moiety is NAlk2 (1a, 2a and 3a), the oxidation process is always
reversible. The oxidation is irreversible for compounds 1c, 2c
and 3c bearing the carbazolyl donor. For these compounds,
oxidation leads to the formation of a new electroactive species
and an irreversible reduction peak, at lower potential (Ep ≈ -0.5
V) is observed on the reverse scan after the first oxidation. For
diphenylamino derivatives 1b and 2b, the formation of a deposit
on the working electrode is occurred after the first oxidation step
and a fine intense signal is observed attributed to the formation
dimerization or polymerization products as described in the
Linear optical properties
The UV/Vis and photoluminesce (PL) spectroscopic data for
compounds 1-3 measured in CHCl3 at room temperature are
presented in Table 2. The analyses were carried out using
low-concentrated solutions of chromophores (0.9-1.7 × 10-5 M).
As representative examples, normalized spectra of compounds
1 are displayed in Figure 3. Compounds 1 and 2 exhibit charge
transfer (CT) absorption band in the UV or purple region with
relatively low molar extinction coefficients around 20 mM-1 cm-1
or below. In each series, the most blue-shifted energetic CT
absorption bands are observed for the carbazoyl derivatives,
whereas the absorption maxima are similar for dialkylamino and
3
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10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
diphenylamino chromophores. This is in agreement with the
electrochemical band gap values. Compounds 1 and 2 exhibit
intense blue-green emission with quantum yield > 0.5. Both
compounds 1b and 2b possess red-shifted emission with
regards to their unsubstituted analogue A,[24c] indicating a
stronger ICT induced by cyanophenyl and trifluoromethylphenyl
substituents. Bathochromic shifts of the absorption and emission
maxima are observed for cyano derivatives 1 as compared their
trifluoromethyl analogues 2, which is in accordance with the
electrochemical behaviour. Diphenylamino derivatives 1b and
2b in each series exhibit the most red-shifted emission, as
observed in other families of similar push-pull compounds.[14b,19]
Compounds 3 are poorly emissive in solution, probably due to
twisted intramolecular charge transfer (TICT) excited state. Only
carbazole derivative 3c exhibits a moderate photoluminescence
quantum yield of 0.10.
observed when the polarity is increased, which is due to the
stabilization of highly polar excited state in polar solvent.[29]
Table 3 displays the emission maxima of compounds 1-3 in a
series of aprotic solvents of different polarity, evaluated
according to the Reichardt polarity scale (ET(30)).[30] Compounds
1-3 do not exhibit significant absorption solvatochromism (less
than 10 nm difference whatever the solvent) was observed
without correlation with solvent polarity. Compounds 1 and 2
exhibit the typical behavior of D-π-A derivatives: for each
compound, the emission maxima is proportional to ET(30) of the
corresponding solvent (Figure S29). Figures 4 and 5 (part A)
display the normalized spectra and color change in various
aprotic solvents upon UV-irradiation of compound 1b. This
compound possesses luminescence from blue in n-heptane to
orange in MeCN. The slope (m) of the regression line of
emission maxima vs ET(30) is a way to roughly evaluate the
ICT.[14c] Compound 1a exhibits the highest m parameter and
compounds 1 show higher m value than the corresponding
compounds 2 indicating higher ICT into cyano derivatives 1 than
into trifluoromethyl analogues. For compounds 3, the
fluorosolvatochromism behavior is different as shown on Figure
4 (part B): in solvents with lower polarity (n-heptane, toluene for
all compounds as well as 1,4-dioxane and THF in case of 3c)
the formation of J-aggregate leading to an emission band in the
550-700 nm range is observed.[31] In higher polarity solvents,
compounds 3 exhibit classical positive fluorosolvatochromism.
The m parameters were calculated using only the data gained
from these solvents. Finally, all compounds are emissive in solid
state with emission going from blue for 1c and 2c to red for 3a
and 3b (Figure 6).
Table 2. UV-Vis and photoluminescence (PL) data of compounds 1-3 in CHCl3
solution.
Comp.
Stokes
λabs
nm
,
ε, mM-1 cm-1
λ
em, nm
ΦF
shift, cm-1
1a
1b
1c
2a
2b
2c
3a
3b
3c
408
402
20.4
20.2
496
531
486
474
517
474
508
494
469
0.63
0.72
4350
6040
6970
4540
5910
8310
1730
2430
6080
363sh
340
8.5
0.64
11.4
390
396
340
14.5
20.9
12.3
0.76
0.75
0.53
Table 3. Fluorosolvatochromism of compounds 1-3 and A in various aprotic
467sh
403
14.1
28.5
17.4
28.8
> 0.01
> 0.01
0.10
solvents and in the solid state.
441sh
398
n-
hep-
tane
Tolu-
ene
1,4-
dio-
THF
DCM
MeCN
45.6 [a]
m[b]
Solid
Comp.
state
[c]
xane
36.0
37.4
40.7
365
29.6
[a]
[a]
30.9
33.9[a]
[a]
[a]
1a
430
457
424
426
454
419
596
573
468
488
446
461
482
441
483
502
460
477
495
454
501
490
536
540
494
512
532
489
511
505
524
554
505
498
544
500
528
517
478
528
604
604
558
563
589
553
564
532
494
559
11.06
9.94
9.08
8.36
9.12
9.02
6.93
4.23
3.71
7.74
502
505
451
469
526
454
664
611
541
1b
1c
2a
2b
2c
485/
670
485/
623
452/
538
3a
3b
3c
456/
562
453/
609
[e]
-
445
[d]
A[23c]
508
[e]
-
[e]
-
[e]
-
[a] ET(30), Reichardt polarity parameter in kcal mol-1.
[b] Slope of the regression line λmax (nm) vs. ET(30) in nm kcal-1.
[c] Powder. [d] in cyclohexane (ET(30) = 30.9). [e] not measured.
Figure 3. Normalized absorption (dashed line) and emission spectra (solid
lines of compounds 1a (green), 1b (blue) and 1c (red) in CHCl3 solution.
Positive fluorosolvatochromism associated with
a
moderate absorption solvatochromism is characteristic of push-
pull fluorophores: a bathochromic shift of the emission band is
4
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10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
scalar product between the permanent dipolar moment of the
molecule ꢀ⃗ in fundamental state and the vector component of
β
[32]
described as β//
.
The results are presented in Table 4. It
values are obtained indicating
should be noted that positive µ
β
that both ground and excited states are polarized in the same
direction and that the excited state is more polarized than
ground state, in accordance with fluorosolvatochromic
observation. The NLO responses of compounds 1-3 remain
moderate mainly due to nonoptimized π-conjugated linkers with
the higher µβ
dialkylamino derivatives exhibit the highest µ
values for compounds 3. In each series, the
value, followed by
β
diphenylamino derivatives (2a and 2b exhibit even similar
values) and the NLO response of carbazole derivatives is
significantly lower, at the detection limit of the used technique. A
comparison of chromophores 1b and 2b with unsubstituted
Figure 4. Normalized emission spectra of 1b in different aprotic solvents.
analogue
A
implies
that
4-cyanophenyl
and
4-
trifluoromethylphenyl electron-withdrawing substituents in C2
position of the quinazoline core significantly enhance the NLO
response. Moreover, the cyano substituted compounds 1 exhibit
significantly higher NLO response than trifluoromethyl
substituted chromophores 2 in accordance with higher Hammett
constant for cyano group. All these results are in full accordance
with the electrochemical and UV-Visible data: NLO responses
increase when absorbance maxima are redshifted and
electrochemical gap decreased.
Table 4. µβ values for compounds 1-3 and A.
Comp.
1a
µ
β
, 10-48 esu [a]
Comp.
2c
µβ
, 10-48 esu [a]
240
140
<40
110
110
<40
280
150
<40
<40
1b
3a
1c
3b
2a
3c
Figure 5. Fluorescence color changes for 1b (part A) and 3c (part B) in
various solvents (from left to right: n-heptane, toluene, 1,4-dioxane, CHCl3,
CH2Cl2 and MeCN). Photographs were taken in the dark upon irradiation with
a hand-held UV lamp (λem = 366 nm)
2b
A
[a] µβ (2ω) at 1907 nm in CHCl3. Molecular concentrations used for the
measurements were in the range of 10-3 to 10-2 M, µ
β ± 10%
Computational studies
Spatial and electronic properties of all target
chromophores 1–3 were investigated at the DFT level by using
the Gaussian® 16 software package.[33] The geometries of
molecules were optimized using the DFT B3LYP/6-311+G(2df,p)
method. Energies of the HOMO and the LUMO, their differences,
ground-state dipole moments μ and first hyperpolarizabilities β
(1907 nm) were calculated on the DFT B3LYP/6-311+G(2df,p)
level including CHCl3 as a solvent (Table 5).
Figure 6. Emission of compounds 1c, 2a, 2b and 3b (from left to right) in solid
state (powder). Photographs were taken in the dark upon irradiation with a
hand-held UV lamp (λem = 366 nm)
The calculated HOMO and LUMO energies are within the
range of –5.86 to –5.19 and –3.04 to –2.24 eV, respectively. The
computed values are in
a
good agreement with the
Second order NLO properties
electrochemically obtained HOMO and LUMO levels as
demonstrated by their correlations (Figures S33-S35 in the ESI).
Hence, the used DFT method can be considered as appropriate.
In all particular series, the HOMO/LUMO decreases within the
order of a→b→c; the differences between chromophores a and
b (NAlk2 vs. NPh2 donors) are relatively small. Carbazolyl-
substituted chromophores showed the largest HOMO–LUMO
The second order NLO properties have been studied in
chloroform solution by the electric-field induced second
harmonic generation (EFISH) method at a non-resonant incident
wavelength of 1907 nm. The second harmonic at
λ = 953 nm is
therefore well clear of the absorption bands of the
chromophores. This method provides the NLO response as the
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
gaps. Figure 7 shows localization of the HOMO(–1/2) and
LUMO(+1/2) as well as Mulliken charges in representative
chromophores 1a and 3a that differ in the arrangement of the
D/A couple and the π-linker extension. As expected, the
HOMO(–1/2) in 1a are mostly spread over the N,N-diethylanilino
donor, while the LUMO(+1/2) occupy the quinazoline,
4-cyanophenylene as well as phenylene moieties. The HOMO(–
1/2)
in
3a
is
represented
by
whole
5-(N,N-
diethylanilino)thiophen-2-yl moiety, the LUMO(+1/2) are centrally
spread over the quinazoline and thiophene rings.
Table 5. DFT calculated data of compounds 1-3
EHOMO
DFT
ELUMO
DFT
∆E
DFT
µ
λmax
TD-DFT
β
(-
E
[D]
2ω,ω,ω)
DFT
HOMO
DFT
Comp.
[eV]
[eV]
[eV]
[nm]
[10-30
esu]
104
139
51
[eV
]
1a
1b
1c
2a
2b
2c
3a
3b
3c
–5.52
–5.53
–5.86
–5.50
–5.51
–5.85
–5.19
–5.33
–5.75
–2.44
–2.54
–2.64
–2.27
–2.24
–2.51
–2.89
–2.97
–3.04
3.08
2.99
3.22
3.22
3.11
3.34
2.30
2.36
2.71
12.89
10.78
9.04
10.63
8.34
6.54
8.92
5.63
3.84
462
476
435
441
459
422
638
609
517
–5.52
–5.53
–5.86
–5.50
–5.51
–5.85
–5.19
–5.33
–5.75
93
125
43
Figure 7. Localization of frontier molecular orbitals and Mulliken charges in
representative chromophores 1a (A) and 3a (B).
587
551
182
All data calculated at the DFT level by using the Gaussian® 16 software
package and DFT B3LYP/6-311+G(2df,p) method in CHCl3. The first
Conclusion
hyperpolarizabilities
β(-2ω,ω,ω) were calculated at 1907 nm. The electronic
In summary, we have designed and synthesized a series of
amino substituted quinazoline push-pull chromophores in which
the electron-withdrawing character of the quinazoline core is
enhanced by electron-deficient groups, their photophysical and
electrochemical properties have been measured. The proposed
combination of D and A provided a series of chromophores with
wide spectral emission range in both solution and solid state.
Compounds with 4-cyanophenyl and 4-trifluoromethylphenyl
substituent in C2 position of the quinazoline core exhibited
enhanced intramolecular charge transfer with regard to their
unsubstituted analogue as shown by their red-shifted absorption
and emission spectra as well as their decreased electrochemical
gap. These compounds are highly luminescent in chloroform
and in the solid state. On the other hand, 4-cyanoquinazolines
are poorly emissive in solution but possess red luminescence in
the solid state. These compounds exhibit moderate second
order NLO response measured by EFISH method. Nevertheless,
electron-withdrawing substituents on the quinazoline core induce
absorption spectra, the longest-wavelength absorption maxima and the
corresponding electron transitions were calculated using TD-DFT (nstates = 8)
B3LYP/6-311+G(2df,p).
The calculated ground state dipole moments range from
3.84 to 12.89 D and reflect the spatial arrangement of the
particular chromophores. In general, the carbazolyl-substituted
chromophores in series c showed the lowest dipole moments,
whereas the N,N-dialkylamino derivatives in series a possess
the largest µ values.
Electronic absorption spectra were calculated using TD-
DFT method and CHCl3 as a solvent. All spectra are listed in the
ESI (Figures S37-S39), the positions of the longest-wavelength
absorption maxima are given in Table 5. In general, the
calculated spectra are red-shifted compared to the experimental;
however, the calculated and experimental λmax values correlate
reasonably (Figure S36). For chromophores 1a-c and 2a-c, the
longest-wavelength band appearing between 400 and 500 nm is
generated by pure HOMO→LUMO transition. Chromophores 3a-
c with inversed D-π-A arrangement showed significantly red-
shifted longest-wavelength band, which may appear as a
shoulder (see the full-range experimental absorption spectra in
the ESI Figure S29). Whereas this red-shifted band corresponds
to the HOMO→LUMO transition, the band localized between
400 and 500 nm is generated by the HOMO→LUMO+1
transition.
a significant enhancement of the µβ value. Optimized π-
conjugated linkers with phenylenevinylene or thienylenevinylene
bridges would probably increase the NLO responses.
Experimental Section
The quadratic hyperpolarizability tensors
β have been also
calculated. A correlation of the experimental and calculated µβ
products (Figure S40) confirms the same trends of both
General Information
quantities. In general, the calculated
β values for diphenylamino
Unless otherwise indicated, all common reagents and solvents were
used from commercial suppliers without further purification. Melting
points were measured on the instrument Boetius. TLC was and column
chromatography was carried out on SiO2. 1H NMR and 13C NMR spectra
were recorded at room temperature at 300 and 75.3 MHz respectively,
on a Bruker AC-300 spectrometer; at 400 and 100 MHz respectively, on
derivatives 1b and 2b are higher than their respective
dialkylamino analogues 1a and 2a. The highest NLO responses
have been calculated for chromophores 3a and 3b similarly as
proved by the aforementioned EFISH method.
6
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10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
a Bruker DRX-400 spectrometer; or at 600 MHz on a Bruker DRX-600
spectrometer (1H NMR spectrum for compound 1c). For compounds 1,
3b,c and 8a mass spectra were recorded on the SHIMADZU GCMS-
QP2010 Ultra instrument with electron ionization (EI) of the sample. For
compounds 2 and 8b, HRMS spectra were performed at the Centre
Régional de Mesures Physiques de l'Ouest" (CRMPO, Université de
Rennes1, Rennes, France) using a Bruker MetroTOF-Q II apparatus.
Microanalyses (C, H, N) were performed using the Perkin–Elmer 2400
elemental analyzer. The absorption and emission spectra were recorded
on Fluoromax-3 spectrophotometer (Jobin-Yvon Horiba). Compounds
were excited at their absorption maxima (band or lower energy) to record
the emission spectra. All solutions were measured with optical densities
below 0.1. Fluorescence quantum yields ( 10%) were determined
relative to 9,10-bisphenylethynylanthracene in cyclohexane (ΦF = 1.00).
Stocks shifts were calculated considering the lowest energetic absorption
band.
2-(4-Trifluoromethylphenyl)quinazoline-3H-one (7b). Was synthesized
by the same approach as 7a. After cooling of reaction mixture the formed
quinazolinone 6b was filtered off and washed with EtOH. Colorless solid,
yield 78%, mp 285–287 °C (mp lit.34 280–282 °C) 1H NMR (300 MHz,
DMSO-d6): δ 7.57 (t, 1H, J = 7.6 Hz, CH quinaz), 7.77 (d, 1H, J = 8.1 Hz,
CH quinaz), 7.87 (t, 1H, J = 7.6 Hz, CH quinaz), 7.93 (d, 2H, J = 8.2 Hz,
C6H4CF3) 8.17 (d, 1H, J = 8.1 Hz), 8.37 (d, 2H, J = 8.2 Hz, C6H4CF3).
Calcd for C15H9F3N2O (290): C 62.07; H 3.13; N 9.65. Found: C 61.98;
H 3.02; N 9.46.
2-(4-Cyanophenyl)-4-bromoquinazoline (8a). Was obtained similar to
described method.25 To a suspension of 2-(4-cyanophenyl)quinazolin-
4(3Н)-one 7a (0.38 g, 1.54 mmol) in toluene (6.8 ml), triethylamine (0.17
ml) and solution of POBr3 (1.75 g, 6.10 mmol) in toluene (3.4 ml) were
added. The reaction mixture was stirred at 80 °С for 24 h. After cooling to
room temperature the precipitate was filtered off, washed with NaHCO3
solution and dried under reduced pressure. Colorless solid, yield 0.58 g
(85%), mp 250–252 °C. 1H NMR (400 MHz, DMSO-d6): δ 7.91 (m, 1H),
8.01 (d, 2H, J = 8.2 Hz, C6H4CN), 8.13 (m, 2H,), 8.24 (d, 1H, J = 8.3 Hz,
CH quinaz), 8.66 (d, 2H, J = 8.2 Hz, C6H4CN). MS (m/z, Irel %): 311
[M+2]+ (23), 309 [M]+ (24), 231 (18), 230 [M-Br]+ (100), 102 (54), 76 (16),
75 (28), 16 (16). Calcd for C15H8BrN3 (310): C 58.09; H 2.60; N 13.55%.
Found: C 58.04; H 2.47; N 13.41.
The electrochemical studies of the compounds were performed in a
with a 3-electrodes cell (WE: Pt, RE: Ag wire, CE: Pt). Ferrocene was
added at the end of each experiment to determine redox potential values.
The potential of the cell was controlled by a µAUTOLAB Type III
potentiostat monitored by a computer. Anhydrous and freshly distilled
dichloromethane was used as solvent and degassed with nitrogen. The
supporting salt used was NBu4PF6 for electrochemical analysis (>99.9 %
Sigma-Aldrich).
2-(4-Trifluoromethylphenyl)-4-bromoquinazoline
(8b).
Was
Experimental details on EFISH measurements are described
elsewhere.[34]
synthesized by the same approach as 8a. After cooling to room
temperature the product was extracted with CH2Cl2 (50 ml), organic layer
was washed with NaHCO3 solution, then concentrated and dried under
reduced pressure. 4-Bromoquinazoline 8b was extracted with hexane,
solvent was removed under reduced pressure, and the product was used
without additional purification. Colorless solid, yield 40%, mp 105–107 °C.
1H NMR (300 MHz, DMSO-d6): δ 7.88–7.97 (m, 3H), 8.16 (d, 2H, J = 3.7
Hz), 8.23 (d, 1H, J = 8.4 Hz, CH quinaz), 8.67 (d, 2H, J = 8.2 Hz,
C6H4CF3). HRMS: found [M+H]+ 352,9896; requires [M+H]+ 352,9896.
Calcd for C15H879BrF3N2 (352): C 51.02; H 2.28; N 7.93. Found: C
50.90; H 2.13; N 7.67%.
Preparation of intermediates
2-Arylquinazoline-4(3H)-ones (7a,b) were synthesized in two steps with
isolation of intermediate (Schiff base 6a or dihydroquinazolinone 6b).
Starting compound 2-(5-bromothiophen-2-yl)-4-cyanoquinazoline 9 was
synthesized as described in our previous work.[27]
2-(4-Cyanobenzylideneamino)benzamide (6a). To a solution of 2-
aminobenzamide
4 (0.50 g, 3.7 mmol) in ethanol (9 mL) 4-
cyanobenzaldehyde (0.54 g 3.7 mmol) was added. After stirring for 30
minute the precipitate started to drop out. The reaction mixture was
summarily stirred during 5 h, and the precipitate was filtered off and
washed with EtOH. Yellow solid, yield 77%, mp 189–191 °C. 1H NMR
(400 MHz, DMSO-d6): δ 7.25 (d, 1H, J = 7.8 Hz, CH benzamide), 7.32 (t,
1H, J = 7.4 Hz, CH benzamide), 7.55 (m, 2H, NH, CH benzamide), 7.84
(d, 1H, J = 7.8 Hz, CH benzamide), 7.97 (br. s, 1H, NH), 8.03 (d, 2H, J =
8.1 Hz, C6H4CN), 8.13 (d, 2H, J = 8.1 Hz, C6H4CN), 8.69 (s, 1H, N=CH).
Calcd for C15H11N3O (249): C 72.28; H 4.45; N 16.86. Found: C 72.21;
H 4.32; N 16.84.
General procedures of Suzuki cross-coupling for the
synthesis of quinazolines 1-3.
General procedure I. A solution of bromoquinazoline 8a or 9 (0.8 mmol)
in toluene (15 ml) was stirred at room temperature for 5 min, then the
corresponding boronic acid or boronic acid pinacol ester (1 mmol),
PdCl2(PPh3)2 (15 mg), PPh3 (11 mg), solution of K2CO3 (0.9 g) in water
(7.5 ml) and EtOH (8 ml) were added. The mixture was stirred at 85 °C
for 7 hours in argon atmosphere in round-bottom pressure flask. After
cooling, the target product was filtered off or isolated from the toluene
solution.
2-(4-Trifluoromethylphenyl)-2,3-dihydroquinazolin-4(1H)-one
(6b).
Was synthesized by the same approach as 6a. Colorless solid, yield 71%,
mp 256–258°C. 1H NMR (300 MHz, DMSO-d6): δ 5.86 (s, 1H, CH), 6.69
(dd, 1H, J = 8.1 Hz, J = 7.3 Hz, CH), 6.76 (d, 1H, J = 8.1 Hz), 7.26 (m, 2H,
CH, NH), 7.61 (dd, 1H, J = 7.3 Hz, J = 1.4 Hz, CH), 7.70 (d, 2H, J = 8.4
Hz, C6H4CF3), 7.77 (d, 2H, J = 8.4 Hz, C6H4CF3), 8.44 (s, 1H, NH).
Calcd for C15H11F3N2O (292): C 61.65; H 3.79; N 9.58. Found: C 61.74;
H 3.62; N 9.51.
General procedure II. To the mixture of the 2-(4-trifluorophenyl)-4-
bromoquinazoline 8b (0.25 mmol) in degassed saturated solution of
Na2CO3 (0.5 mL), ethanol (0.5 mL) and toluene (7.5 mL) the appropriate
arylboronic acid (0.5 mmol) and Pd(PPh3)4 (0.025 mmol) were added.
The solution was heated under reflux for 24 h under nitrogen atmosphere.
The reaction mixture was cooled and mixture EtOAc/water (1/1, 10 mL)
was added. The organic layer was separated and the aqueous layer was
extracted with additional EtOAc (2 × 10 mL). The combined organic
extracts were dried over MgSO4 and the solvent was evaporated under
reduced pressure.
2-(4-Cyanophenyl)quinazoline-3H-one (7a). 2-(4-Cyanobenzyliden-
amino)benzamide 6a (0.62 g, 2.5 mmol) was dissolved in ethanol (10
mL), CuCl2 (0.55 g, 4.1 mmol) was added and reaction mixture was
refluxed for 2 h. After cooling the formed quinazolinone 6a was filtered off
and recrystallized from DMSO. Colorless solid, yield 60%, mp 276–
278 °C (mp lit.[35] 280–282 °C) 1H NMR (400 MHz, DMSO-d6): δ 7.57 (m,
1H), 7.79–7.87 (m, 2H), 8.05 (m, 2H), 8.17 (br. s, 1H), 8.34 (m, 2H),
12.74 (s, 1H, NH). Calcd for C15H9N3O (247): C 72.87; H 3.67; N 16.99.
Found: C 72.68; H 3.54; N 16.89.
2-(4-Cyanophenyl)-4-(4-diethylaminophenyl)quinazoline
(1a).
Synthesis was accomplished following the general procedure I. The
product was purified by column chromatography (SiO2, gradually from
hexane/EtOAc (10/1) to hexane/EtOAc (1/1)). Yellow solid, yield 69%,
mp 155–157 °C. 1H NMR (400 MHz, CDCl3): δ 1.27 (t, 6H, J = 7.0 Hz, 2(-
7
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10.1002/ejoc.202000870
European Journal of Organic Chemistry
FULL PAPER
CH3)), 3.49 (q, 4H, 2CH2, J = 7.0 Hz), 6.85 (d, 2H, C6H4NEt2, J = 8.2 Hz),
7.58 (t, 1H, CH quinaz, J = 7.6 Hz,), 7.80 (d, 2H, C6H4CN, J = 7.9 Hz),
7.88 (m, 3H), 8.11 (d,1H, CH quinaz, J = 8.3 Hz), 8.32 (d, 1H, CH quinaz,
J = 8.3 Hz), 8.83 (d, 2H, C6H4CN, J = 7.9 Hz). 13C NMR (100 MHz,
CDCl3): 12.76 (2C, 2CH3), 44.68 (2C, 2(CH2)), 111.27 (2C, CH), 113.47
(C) , 119.27 (C), 121.96 (C), 123.89 (C), 127.35 (CH), 127.69 (CH),
129.18 (2C, CH), 129.23 (CH), 132.33 (4C, CH), 133.49 (CH), 143.03 (C),
149.64 (C), 152.16 (C), 158.23 (C), 168.21 (C). MS (m/z, Irel %): 379
[M+H]+ (14), 378 [M]+ (47), 364 (28), 363 [M-CH3]+ (100), 335 (16), 230
(13), 181 (11), 102 (13). Calcd for C25H22N4 (378): C 79.34; H 5.86; N
14.80. Found: C, 79.41; H, 5.69; N, 14.55%;
7.37 (m, 4H), 7.60 (t, 1H, CH quinaz, J = 7.6 Hz), 7.77 (d, 2H, C6H4CF3, J
= 8.2 Hz), 7.81 (d, 2H, C6H4NPh2, J = 8.9 Hz), 7.91 (t, 1H, CH quinaz, J =
7.6 Hz), 8.15 (d, 1H, CH quinaz, J = 8.4 Hz), 8.27 (d, 1H, CH quinaz, J =
8.2 Hz), 8.81 (d, 2H, C6H4CF3, J = 8.2 Hz). 13C NMR and JMOD (75 MHz,
CDCl3): 121.76 (CH), 122.00 (C), 124.19 (CH), 124.51 (q, J = 272.1 Hz,
CF3), 125.53 (q, J = 3.9 Hz, CH), 125.64 (CH), 127.34 (CH), 127.50 (CH),
129.04 (CH), 129.44 (CH), 129.70 (CH), 130.35 (C), 131.64 (CH), 131.89
(C), 132.32 (C), 133.75 (CH), 141.89 (C), 147.27 (C), 150.19 (C), 152.22
(C), 158.94 (C), 167.96 (C). HRMS: found [M+H]+ 518.1844; requires
[M+H]+ 518.1839. Calcd for C33H22F3N3 (517): C 76.58; H 4.28; N 8.12.
Found: C 76.53; H 4.08; N 8.01.
2-(4-Cyanophenyl)-4-(4-diphenylaminophenyl)quinazoline
(1b).
2-(4-Trifluoromethylphenyl)-4-(4-(9H-carbazol-9-
Synthesis was accomplished following the general procedure I. The
product was purified by column chromatography (SiO2, gradually from
hexane/CHCl3 (5/1) to CHCl3).Yellow solid, yield 74%, mp 205–207 °C.
1H NMR (400 MHz, CDCl3): δ 7.13 (t, 2H, NPh2, J = 7.3 Hz), 7.24 (m, 6H),
7.35 (t, 4H, NPh2, J = 7.3 Hz), 7.62 (t, 1H, CH quinaz, J = 7.6 Hz), 7.81 (d,
4H, J = 7.8 Hz), 7.92 (t, 1H, CH quinaz, J = 7.6 Hz,), 8.15 (d, 1H, CH
quinaz, J = 8.3 Hz), 8.28 (d, 1H, CH quinaz, J = 8.3 Hz), 8.82 (d, 2H,
C6H4CN, J = 7.9 Hz). 13C NMR (100 MHz, CDCl3): 113.70, 119.16,
121.64, 121.99, 124.23, 125.64, 127.36, 127.78, 129.19, 129.42, 129.70,
130.07, 131.61, 132.41, 133.87, 142.67, 147.17, 150.25, 152.11, 158.31,
167.99. MS (m/z, Irel%): 475 [M+H]+ (37), 474 [M]+ (100), 473 (32), 306
[M-NPh2]+ (22), 237 (11), 102 (13), 76 (11). Calcd for C33H22N4 (474): C
83.52; H 4.67; N 11.81. Found: C 83.37; H 4.50; N 11.72.
yl)phenyl)quinazoline (2c). Synthesis was accomplished following the
general procedure II. The product was purified by column
chromatography (SiO2, petroleum ether/EtOAc, 9/1) and recrystallization
from the mixture of CH2Cl2/heptane three times. Colorless solid, yield
39%, mp 212-214 °C. 1H NMR (300 MHz, CDCl3): δ 7.35 (t, 2H, CH
carbazole, J = 7.6 Hz), 7.48 (t, 2H, CH carbazole, J = 7.6 Hz), 7.61 (d,
2H, J = 8.1 Hz), 7.70 (t, 1H, CH quinaz, J = 7.6 Hz), 7.80–7.88 (m, 4H),
7.99 (t, 1H, CH quinaz, J = 7.6 Hz), 8.16–8.26 (m, 5H), 8.32 (d, 1H, CH
quinaz, J = 8.2 Hz), 8.87 (d, 2H, C6H4CF3, J = 8.1 Hz). 13C NMR and
JMOD (75 MHz, CDCl3): 110.00 (CH), 120.56 (CH), 120.63 (CH), 122.06
(C), 123.92 (C), 124.20 (q, J = 272.9 Hz, CF3), 125.65 (q, J = 3.9 Hz, CH),
126.33 (CH), 127.02 (CH), 127.14 (CH), 128.04 (CH), 129.13 (CH),
129.70 (CH), 132.01 (CH), 134.19 (CH), 136.40 (C), 139.90 (C), 140.78
(C), 141.61 (C), 152.27 (C), 159.11 (C), 167.73 (C). HRMS: found [M+H]+
516,1685; requires [M+H]+ 516,1682. Calcd for C33H20F3N3 (515): C
76.88; H 3.91; N 8.15. Found: C 76.68; H 3.72; N 8.09.
2-(4-Cyanophenyl)-4-(4-(9H-carbazol-9-yl)phenylaminophenyl)-
quinazoline (1c). Synthesis was accomplished following the general
procedure I. After cooling and partially evaporating of reaction mixture
the precipitate was filtered off and washed with hexane. Colorless solid,
yield 84%, mp 235–237 °C. 1H NMR (600 MHz, DMSO-d6): δ 7.34 (t, 2H,
CH carbazole, J = 7.5 Hz), 7.49 (t, 2H, CH carbazole, J = 7.5 Hz), 7.62 (d,
2H, J = 7.7 Hz), 7.84 (t, 1H, CH quinaz, J = 7.6 Hz), 7.94 (d, 2H, J = 8.2
Hz), 8.05 (d, 2H, J = 8.2 Hz), 7.84 (t, 1H, CH quinaz, J = 7.6 Hz), 8.23 (m,
3H), 8.28 (m, 2H), 8.37 (d, 1H, CH quinaz, J = 8.2 Hz), 8.83 (d, 2H,
C6H4CN, J = 8.4 Hz). 13C NMR (100 MHz, CDCl3): 109.95, 113.99,
119.10, 120.61, 120.63, 122.05, 123.90, 126.32, 127.05, 127.11, 128.34,
129.27, 129.70, 131.98, 132.53, 134.33, 136.19, 139.96, 140.69, 142.38,
152.18, 158.51, 167.79. MS (m/z, Irel%): 473 [M+H]+ (37), 472 [M]+ (100),
471 (28), 306 [M-carbazole]+ (25), 236 (22), 102 (11), 76 (18). Calcd for
C33H20N4 (472): requires C 83.88; H 4.27; N 11.86. Found: C 83.68; H
4.09; N 11.75.
2-(5-(4-Diphenylaminophenyl)thiophen-2-yl)-4-cyanoquinazoline (3b).
Synthesis was accomplished following the general procedure I. The
product was purified by column chromatography (SiO2, hexane/EtOAc,
5/1). Orange solid, yield 28%, mp 220–222 °C. 1H NMR (400 MHz,
CDCl3): δ 7.06–7.18 (m, 7H), 7.27–7.33 (m, 6H), 7.60 (d, 2H, J = 8.1 Hz),
7.70 (t, 1H, CH quinaz, J = 7.5 Hz), 7.98 (t, 1H, CH quinaz, J = 7.5 Hz),
8.07 (d, 1H, CH quinaz. J = 8.3 Hz), 8.12 (d, 1H, H-3’ thioph, J = 4.0 Hz),
8.19 (d, 1H, CH quinaz, J = 8.2 Hz). 13C NMR (100 MHz, CDCl3): 114.36,
122.71, 123.18, 123.65, 123.68, 125.04, 125.28, 126.94, 127.61, 128.90,
129.01, 129.56, 132.11, 136.07, 139.82, 143.52, 147.42, 148.41, 150.40,
151.89, 157.98. MS (m/z, Irel%): 482 [M+2]+ (11), 481 [M+1]+ (36), 480
[M]+ (100), 240 (12). Calcd for C31H20N4S (480): C 77.48; H 4.19; N 11.66.
Found: C 77.41; H 3.99; N 11.48.
2-(4-Trifluoromethylphenyl)-4-(4-dimethylaminophenyl)quinazoline
(2a). Synthesis was accomplished following the general procedure II. The
product was purified by column chromatography (SiO2, petroleum
ether/EtOAc, 9/1). Yellow solid, yield 77%, mp 160-162 °C (mp lit.[36]
136−138 °C).1H NMR (300 MHz, CDCl3): δ 1.55 (s, 6H, 2CH3), 6.89 (d,
2H, C6H4NMe2, J = 8.3 Hz), 7.57 (t, 1H, CH quinaz, J = 7.8 Hz), 7.82 (d,
2H, C6H4CF3, J = 8.0 Hz), 7.86-7.93 (3H, m), 8.13 (d, 1H, CH quinaz, J =
8.4 Hz), 8.29 (d, 1H, CH quinaz, J = 8.4 Hz), 8.82 (d, 2H, C6H4CF3, J =
8.0 Hz). 13C NMR and JMOD (75 MHz, CDCl3): 40.42 (CH3), 111.94 (CH),
122.05 (C), 124.51 (q, J = 272.9 Hz, CF3), 125.15 (C), 125.46 (q, J = 3.9
Hz, CH), 127.17 (CH), 127.61 (CH), 129.03 (CH), 129.30 (CH), 131.74
(CF3), 132.01 (CH), 133.44 (CH), 142.15 (C), 152.09 (C), 152.26 (C),
158.88 (C), 168.28 (C). HRMS: found [M+H]+ 394.1527; requires [M+H]+
394.1526. Calcd for C23H18F3N3 (393): C 70.22; H 4.61; N 10.68. Found:
C 70.04; H 4.41; N 10.46.
2-(5-(4-(9H-Carbazol-9-yl)phenyl)thiophen-2-yl)-4-cyanoquinazoline
(3c). Synthesis was accomplished using the 9H-carbazole-9-(4-
phenyl)boronic acid pinacol ester as a reagent following the general
procedure I. The reaction was carried out for 20 hours. After cooling of
reaction mixture the precipitate was filtered off and washed with hexane.
Yellow solid, yield 35%, mp 255–257 °C. 1H NMR (400 MHz, CDCl3): δ
7.32 (t, 2H, CH carbazole, J = 7.4 Hz), 7.42–7.52 (m, 5H), 7.66 (d, 2H, J
= 7.8 Hz), 7.75 (t, 1H, CH quinaz, J = 7.6 Hz), 7.96 (d, 2H, J = 8.0 Hz),
8.02 (t, 1H, CH quinaz, J = 7.6 Hz), 8.11–8.17 (m, 3H), 8.22 (m, 2H). 13
C
NMR (100 MHz, CDCl3): 109.94, 114.34, 120.35, 120.53, 122.88, 123.71,
125.15, 125.33, 126.22, 127.52, 127.65, 128.38, 129.11, 132.03, 133.03,
136.30, 140.80, 141.49, 143.61, 149.08, 151.86, 157.79. MS (m/z, Irel%):
480 [M+2]+ (11), 479 [M+1]+ (35), 478 [M]+ (100), 239 (18), 76 (17). Calcd
for C31H18N4S (478): C 77.80; H 3.79; N 11.71. Found: C 77.58; H 3.74;
N 11.82.
2-(4-Trifluoromethylphenyl)-4-(4-diphenylaminophenyl)quinazoline
(2b). Synthesis was accomplished following the general procedure II.
The product was purified by column chromatography (SiO2, petroleum
ether/EtOAc, 19/1). Yellow solid, yield 85%, mp 146-148 °C. 1H NMR
(300 MHz, CDCl3): δ 7.13 (t, 2H, NPh2, J = 7.1 Hz), 7.24 (m, 6H), 7.32–
Acknowledgements
This work was supported by the Russian Foundation for Basic
Research (grant numbers 18-03-00112, 19-33-90014).
8
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European Journal of Organic Chemistry
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[15] C. Hadad, S. Achelle, I. López-Solera, J. C. García-Martínez, J.
Rodríguez-López, Dyes Pigm. 2013, 97, 230-237.
Analytical studies were carried out using equipment of the
Centre for Joint Use «Spectroscopy and Analysis of Organic
Compounds» at the Postovsky Institute of Organic Synthesis of
the Russian Academy of Sciences (Ural Branch).
[16] a) E. V. Verbitskiy, A. A. Baranova, K. I. Lugovik, M. Z. Shafirov, K. O.
Khokhlov, E. M. Cheprakova, G. L. Rusinov, O. N. Chupakhin, V. N.
Charushin, Anal. Bioanal. Chem. 2016, 408, 4093-4101; b) E. V.
Verbitskiy, E. M. Dinastiya, A. A. Baranova, K. O. Khokhlov, R. D.
Chuvashov, Y. A. Yakhovleva, N. I. Makarova, E. V. Vetrovz, A. V.
Metelitsa, P. A. Slepukhin, G. L. Rusinov, O. N. Chupakhin, V. N.
Charushin, Dyes Pigm. 2018, 159, 35-44.
Keywords: quinazoline • push-pull derivatives • intramolecular
charge transfer • nonlinear chromophores • fluorescence
[17] a) L. Li, J. Ge, H. Wu, Q.-H. Xu, S. Q. Yao, J. Am. Chem. Soc. 2012,
134, 12157-12167; b) Z. Na, L. Li, M. Uttamchandani, S. Q. Yao,
Chem. Commun. 2012, 48, 7304-7306; c) B. Liu, H.-L. Zhang, J. Liu,
Y.-D. Zhao, Q.-M. Luo, Z.-L. Huang, J. Mater. Chem. 2007, 17, 2921-
2929; d) L. Li, Y. Tian, J. Yang, P. Sun, J. Wu, H. Zhou, S. Zhang, B.
Jin, X. Xing, C. Wang, M. Li, G. Cheng, H. Tang, W. Huang, X. Tao, M.
Jiang, Chem. Asian J. 2009, 4, 668-680; e) L. Hu, S. Hussain, T. Liu, Y.
Yue, J. Liu, Y. Tian, X. Tian, New J. Chem. 2018, 42, 14725-14728.
[18] S. Achelle, A. Barsella, C. Baudequin, B. Caro, F. Robin-le Guen, J.
Org. Chem. 2012, 77, 4087-4096.
[1]
[2]
F. Bureš, RSC Adv. 2014, 4, 58826-58851.
M. Klikar, F. Bureš, O. Pytela, T. Mikysek, Z. Padělková, A. Barsella, K.
Dorkenoo, S. Achelle, New J. Chem. 2013, 37, 4230-4240.
a) J. F. Callan, A. P. de Silva, D. C. Magri, Tetrahedron 2005, 61, 8551-
8588; b) B. Valeur, I. Leray, Coord. Chem. Rev. 2000, 205, 3-40; c) J.
Wu, W. Liu, J. Ge, H. Zhang, P. Wang, Chem. Soc. Rev. 2011, 40,
3483-3495.
[3]
[4]
[5]
a) J.-M. Ji, H. Zhou, K. Hwan, J. Mater. Chem. A 2018, 6, 14518-
14545; b) A. Carella, F. Borbone, R. Centore, Front. Chem. 2018, 6,
481; c) A. Mahmood, Solar Energy 2016, 123, 127-144; d) Y. Lin, Y. Li,
X. Zhang, Chem. Soc. Rev. 2012, 41, 4245-4272.
[19] S. Achelle, A. Barsella, B. Caro, F. Robin-le Guen, RSC Adv. 2015, 5,
39218-39227.
a) S.-H. Chou, H.-W. Kang, S.-T. Chang, K.-Y. Wu, G. C. Bazan, C.-L.
Wang, H.-L. Lin, J.-H. Chang, H.-W. Lin, Y.-C. Huang, C.-S. Tsao, K.-T.
Wong, ACS Appl. Mater. Interfaces 2016, 8, 18266-18276; b) I. Cho, S.
K. Park, B. Kang, J. W. Chung, J. H. Kim, W. S. Yoon, K. Cho, S. Y.
Park, J. Mater. Chem. C 2016, 4, 9460-9468; c) D. Bharath, S.
Chithiravel, M. Sasikumar, N. R. Chereddy, B. Shanigaram, K.
Bhanuprakash, K. Krishnamoorthy, R. V. Juyathirtha, RSC Adv. 2015,
5, 94859-94865.
[20] a) R. J. Durand, S. Gauthier, S. Achelle, S. Kahlal, J.-Y. Saillard, A.
Barsella, L. Wojcik, N. le Poul, F. Robin-le Guen, Dalton Trans. 2017,
46, 3059-3069; b) R. J. Durand, S. Gauthier, S. Achelle, T. Groizard, S.
Kahlal, J.-Y. Saillard, A. Barsella, N. le Poul, F. Robin-le Guen, Dalton
Trans. 2018, 47, 3965-3975.
[21] a) S. Achelle, S. Kahlal, A. Barsella, J.-Y. Saillard, X. Che, J. Vallet, F.
Bureš, B. Caro, F. Robin-le Guen, Dyes Pigm. 2015, 113, 562-570; b)
R. J. Durand, S. Achelle, S. Gauthier, N. Cabo, M. Ducamp, S. Kahlal,
J.-Y. Saillard, A. Barsella, F. Robin-le Guen, Dyes Pigm. 2018, 155, 68-
74.
[6]
a) C. Cao, W.-C. Chen, S. Tian, J.-X. Chen, Z.-Y. Wang, X.-H. Zheng,
C.-W. Ding, J.-H. Li, J.-J. Zhu, Z.-L. Zhu, Q.-X. Tong, C.-S. Lee, Mater.
Chem. Front. 2019, 3, 1071-1079; b) X. Qiu, S. Ying, C. Wang, M.
Hanif, Y. Xu, Y. Li, R. Zhao, D. Hu, D. Ma, Y. Ma, J. Mater. Chem. C
2019, 7, 592-600; c) J. Wang, C. Liu, C. Jiang, C. Yao, M. Gu, W.
Wang, Org. Electron. 2019, 65, 170-178.
[22] a) H. Akdas-Kilig, T. Roisnel, I. Ledoux,; H. le Bozec New J. Chem.
2009, 33, 1470-1473; b) H. Akdas-Kilig, M. Godfroy, J.-L. Fillaut, B.
Donnio, B. Heinrich, P. Kedziora, J.-P. Malval, A. Spangenberg, S. van
Cleuvenbergen, K. Clays, F. Camerel, J. Phys. Chem. C 2015, 119,
3697-3710; c) S. van Cleuvenbergen, P. Kedziora, J.-L. Fillaut, T.
Verbiest, K. Clays, H. Akdas-Kilig, F. Camerel, Angew. Chem. Int. Ed
2017, 56, 9546-9550.
[7]
[8]
G. Aka, H. A. Kahn, D. Vivien, J. M. Benitez, F. Salin, J. Godard, Eur. J.
Solid State Inorg Chem. 1996, 33, 727-736.
a) P. J. Campagnola, M. D. Wei, A. Lewis, L. N. Loew, Biophys. J.
1999, 77, 3341-3349; b) W. Mohler, A. C. Milard, P. J. Campagnola,
Methods 2003, 29, 97-109.
[23] E. V. Nosova, S. Achelle, G. N. Lipunova, V. N. Charushin, O. N.
Chupakhin, Russ. Chem. Rev. 2019, 88, 1128-1178.
[9]
a) T. Taniuchi, S. Okadaand, H. Nakanishi, Appl. Phys. Lett. 2004, 95,
5984-5988; b) T. Taniuchi, S. Ikeda, S. Okada, H. Nakanishi, Jpn J.
Appl. Phys. 2005, 44, L652-L654; c) A. Schneider, M. Neis, M. Stillhart,
B. Ruiz, R. U. A. Khan, P. Gunter, J. Opt. Soc. Am. B, 2006, 23, 1822-
1835; d) Z. Yang, L. Mutter, M. Stillhart, B. Ruiz, S. Aravazhi, M.
Jazbinsek, A. Schneider, V. Gramlich, P. Gunter, Adv. Funct. Mater.
2007, 17, 2018-2023.
[24] a) E. V. Nosova, T. N. Moshkina, G. N. Lipunova, D. S. Kopchuk, P. A.
Slepukhin, I. V. Baklanova, V. N. Charushin, Eur. J. Org. Chem. 2016,
2876-2881; b) D. Liu, Z. Zhang, H. Zhang, Y. Wang, Chem. Commun.
2013, 49, 10001-10003; c) S. Achelle, J. Rodríguez-López, F. Robin-le
Guen, J. Org. Chem. 2014, 79, 7564-7571.
[25] E. V. Nosova, T. N. Moshkina, G. N. Lipunova, E. S. Kelbysheva, N. M.
Loim, P. A. Slepukhin, V. N. Charushin, I. V. Baklanova, Mendeleev
Commun. 2018, 28, 33-35.
[10] C. Moreno-Yruela, J. Garín, S. Orduna, E. Quintero, J. T. López
Navarrete, B. E. Diosdado, B. Villacampa, J. Casado, R. Andreu, J.
Org. Chem. 2015, 80, 12115-12128.
[26] M. Tímea, F. Miklós, L. Lázár, F. Fülöp, ARKIVOC 2016, vi, 247-258.
[27] E. V. Nosova, T. N. Moshkina, G. N. Lipunova, I. V. Baklanova, D. S.
Kopchuk, P. A. Slepukhin, V. N. Charushin, Mendeleev Commun. 2018,
28, 14-16.
[11] Y. Wen, W. Wu, Y. Li, Y. Li, T. Qin, Y. Tang, L. Wang, J. Zhang, Org.
Electron. 2016, 38, 61-68
[12] a) C. Katan, F. Terenziani, O. Mongin, M. H. V. Wertz, L. Porres, T.
Pons, J. Mertz, S. Tretik, M. Blnchard-Desce J. Phys. Chem. A 2005,
109, 3024-3037; b) D. Cvejn, E. Michail, K. Seintis, M. Klikar, O. Pytela,
T. Mikysek, N. Almonasy, M. Ludwig, V. Giannetas, M. Fakis, F. Bureš,
RSC Adv. 2016, 6, 12619-12828; c) E. Çatal, E. Keleş, N. Seferoğlu, S.
Achelle, A. Barsella, F. Robin-le Guen, Z. Seferoğlu, New J. Chem.
2018, 42, 15052-15060.
[28] a) M.-K. Leung, M.-Y. Chou, Y. O. Su, C. L. Chiang, H.-L. Chen, C. F.
Yag, C.-C. Yang, C.-C. Lin H.-T. Chen, Org. Lett. 2003, 5, 839-842; b)
P. Panter, A. Swist, P. Zassowski, M. Lapkowski, P. Data,
Electrochimica Acta 2017, 257, 192-202.
[29] a) H. Detert, V. Schmidt, J. Phys. Org. Chem. 2004, 17, 1051-1056; b)
C. Katan, M. Charlot, O. Mongin, C. Le Droumaguet, V. Jouikov, F.
Terenziani, E. Badaeva, S. Tretiak, M. Blanchard-Desce, J. Phys.
Chem. B 2010, 114, 3152-3169; c) R. Lartia, C. Allain, G. Bordeau, F.
Schmidt, C. F. Fiorini-Debuisschert, M.-P. Teulade-Fichou, J. Org.
Chem. 2008, 73, 1732-1744.
[13] a) S. Achelle, N. Plé, Curr. Org. Synth. 2012, 9, 163-187; b) S. Achelle,
J. Rodríguez-López, F. Robin-le Guen, ChemistrySelect 2018, 3, 1852-
1886; c) G. N. Lipunova, E. V. Nosova, V. N. Charushin, O. N.
Chupakhin, Curr. Org. Synth. 2018, 15, 793-814.
[30] C. Reichardt, Chem. Rev. 1994, 94, 2319-2358.
[14] a) J. Rodriguez-Aguilar, M. Vidal, C. Pastenes, C. Aliaga, M. C.
Rezende, M. Dominguez, Photochem. Photobiol. 2018, 94, 110-1108;
b) M. Fecková, P. le Poul, F. Robin-le Guen, T. Roisnel, O. Pytela, M.
Klikar, F. Bureš, S. Achelle, J. Org. Chem. 2018, 83, 11712-11726; c)
S. Achelle, J. Rodríguez-López, M. Larbani, R. Plaza-Pedroche, F.
Robin-le Guen, Molecules 2019, 24, 1742.
[31] a) A. P. Deshmukh, D. Koppel, C. Chuang, D. M. Cadena, J. Cao, J. R.
Caram, J. Phys. Chem. C 2019, 123, 18702-18710; b) T. Brixner, R.
Hildner, J. Köhler, C. Lambert, F. Würthner, Adv. Energy Mater. 2017, 7,
1700236.
9
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FULL PAPER
[32] a) K. D. Singer, A. F. Garito, J. Chem. Phys., 1981, 75, 3572; (b) B. F.
Levine, C. G. Bethea, Appl. Phys. Lett., 1974, 24, 445; (c) I. Ledoux, J.
Zyss, Chem. Phys., 1982, 73, 203-213.
[33] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb,
J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H.
Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko,
R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov,
J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J.
Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G.
Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara,
K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery Jr., J. E.
Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N.
Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K.
Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M.
Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R.
L. Martin, K. Morokuma, O. Farkas, J. B. Foresman and D. J. Fox,
Gaussian 16, Revision A.03, Gaussian, Inc., Wallingford, CT, 2016.
[34] G. Ulrich, A. Barsella, A. Boeglin, S. Niu, R. Ziessel, ChemPhysChem,
2014, 15, 2693-2700.
[35] M. Abdullaha, S. Mohammed, M. Ali, A. Kumar, R.A. Vishwakarma, S.
B. Bharate, J. Org. Chem., 2019, 84, 5129-5140.
[36] X. Wang, D. He, Y. Huang, Q. Fan, W. Wu, H. Jiang, J. Org.
Chem., 2018, 83, 10, 5458–5466
.
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Entry for the Table of Contents
Chromophores: 4-Сyanoquinazoline, 2-(4-cyanophenyl)quinazoline and 2-(4-trifluorophenyl)quinazoline chromophores bearing 5-(4-
aminophenyl)thiophen-2-yl or 4-aminophenyl electron-donor (D) units have been synthesized. Data of UV-Vis and emission spectroscopy,
cyclic voltammetry, electric field induced second harmonic generation (EFISH) method and quantum-chemical calculations for all compounds
have been analyzed.
11
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