NEW QUINAZOLINE AND QUINOXALINE DERIVATIVES AS A BASE
OF MATERIALS FOR ORGANIC ELECTRONIC DEVICES
Moshkina T. N., Nosova E. V.
Department of Organic and Biomolecular Chemistry, Chemical Technology Institute, Ural Federal University, 620002 Ekaterinburg, Mira Str.
19; +7(965)5263788; e-mail: tan.moshckina@yandex.ru
-conjugated systems
with push-pull architecture
Project aim: design and synthesis of new organic chromophores
as the basis of materials for electronic devices.
Project tasks:
- the synthesis and study of photophysical properties of V-shaped
chromophores based on 2,3-bis(5-arylthiophen-2-yl)quinoxalines;
- development of approaches to the functionalization of the new 2,4disubstituted quinazolines by introduction cyano-groups and donor
substituents; estimation of NLO properties for new compounds;
- the synthesis of novel BF2-complexes based on N,O-ligands;
- carrying out the complex of physical and chemical investigations for the
elucidation of the structure of molecules.
Methods:
Target chromophores have been synthesized through bromination at
thenyl moiety or at position 4 of quinazoline core and subsequent
palladium-catalyzed cross-coupling Suzuki reactions.
BF2 complexes have been obtained by treatment of N,O-ligands with
boron trifluoride etherate in a mixture of toluene and acetic acid.
The structures of target compounds were confirmed by set of modern
physical and chemical methods of analysis: 1Н, 13С, 19F, 11B NMRspectroscopy, mass-spectrometry as well as X-ray analysis.
Photophysical properties were studied by absorption and fluorescence
spectroscopy. The influence of solvent polarity on photophysical
properties was investigated. The effect of protonation was studied by
addition of TFA acid. The quantum yields of BF2 complexes in solid state
were measured by the integrating sphere.
The potential use of molecules as materials with NLO properties will be
evaluated using the EFISH (electric field induced second harmonic
generation) method in collaboration with French science group (Rennes
Universiry).
D
D
CN
N
S
N
N
N
S
N
N
D
S
CN
D
R
N
N
R
1
quinazoline
2
N
R
N
R
3
quinoxaline
Ph
O
X
N
NH
R
N
N
5
R
N
F B
O
F
F B
O
F
R
4
R
5
N
F B
O
F
4
Boron complexes
based on N,O-ligands
Results:
BF2 complexes based on N,O-ligands
V-shaped quinoxalines
S
NH2
+
NH2
1
S
1. EtOH, t
2. NBS, DMF, r.t.
3. cross-coupling*
O
NH
N
NH
N
S
3a-d
S
N
N
*
N
*
F
cross-coupling*
N
N
S
N
3b
Solvent
3a
3b
3c
3d
toluene
MeCN
toluene
MeCN
toluene
MeCN
toluene
MeCN
Ar
λem,
nm
557
519
629
498
578
480
529
R
11a,b
11b
R = H (a), t-Bu (b)
N
N
*
X
O
3d
3c
6a
*Cross-coupling: arylboronic acid or arylboronic acid pinacol ester, PdCl 2(PPh3)2,
PPh3, K2CO3, toluene, EtOH, argon, 85 °C.
λabs,
nm
327, 377, 438
330, 369, 439
301, 424
364, 416
305, 354, 418
348, 409
330, 342, 389
341, 383
O
N
*
Ar = *
3a
S
6a,b
5
4
B
F
N
Br
R
N
CN
CN
S
N
Ar
Ar =*
1. KCN, DMF,
MePhSO3Na, 95 0C
2. NBS, DMF,
80 0C
O
O
2
O
2,4-disubstituted CN-containing quinazolines
Ar
Δvst,
cm-1
3833
4317
8140
2739
7149
3721
7687
ϕ, %
[a]
7
0
14
<1
8
2
11
5
6a toluene
MeCN
NH2
12
6a
Solvent
H
λabs,
nm
402
397
λem,
nm
471
539
ϕ,
%[a]
<1
<1
N
N
R
N
R
O
Δvst,
cm-1
3644
6636
AcONH4, I2
EtOH, 80 0C X
+
F B
HO
13
R
F
R
14
R
N
HO
O
R
15a-d
12: X = H (a), Cl (b); 13: R = H (a), t-Bu (b);
14, 15: X = H, R = H (a); X = Cl, R = H (b);
X = H, R = t-Bu (c); X=Cl; R = t-Bu (d).
[a] 3-aminophthalimide in ethanol as standard.
Br
O
O
NH2
NH2
7
1. CuCl2, EtOH
Br
2. POBr3, NEt3,
toluene
Ar
cross-coupling*
8
HO
N
N
+
b-cyclodextrine
N
H2O, MeOH
N
N
F
HO
1
CN
CN
9
N
BF3(OEt)2, AcOH,
toluene, t
NH2
N
O
N
16
N
H +
[a] 3-aminophthalimide in ethanol as standard.
Absorption (a) and emission (b) color changes
6b
BF3(OEt)2,
AcOH,
toluene, t X
17
NH2
18
B O
F
10a-c
CN
Ar =
N
*
N
*
N
*
S
10a
N
*Cross-coupling: arylboronic acid or arylboronic acid
°
PdCl2(PPh3)2, PPh3, K2CO3, toluene, EtOH, argon, 85 C.
N
3a
3b
a
b
without TFA (1)
135 equiv of TFA (2)
3500 equiv of TFA (3)
6a
S
a
b
without TFA (1)
7000 equiv of TFA (2)
10b
10c
pinacol
15c
ester,
N
Possible practical applications
Changes in the emission spectra of toluene solution of 3a upon the
addition of TFA
The studied compounds are of great value for
further application as materials for optical
devices. Such materials have potential
applications in modulation of optical signals,
medicine, spectroscopic and electrochemical
sensing, microfabrication and imaging, laser
technology, data storage, telecommunication etc.
11a
11b
15a
15b
15c
15d
18
15d
λabs,
nm
354
366
386
395
410
420
407
18
toluene
λem,
ϕ,
nm
%[a]
423
24
441
42
529
1.3
542
0.8
565
0.2
552
0.1
530
8.6
Δvst,
cm-1
4608
4647
6607
6866
6691
5694
5702
solid state
λabs,
ϕ,
nm
%
500
18.5
469
66.3
502
0.2
500
11.1
541
1.9
540
2.5
-
[a] quinine sulfate in 0.1 M H2SO4 as standard
11a
11b
15a
15b
15c 15d
18