Copper-containing copolymers based on the norbornene monomers. Synthesis, photo-, and electroluminescent properties

Article abstract of DOI:10.1134/S107036321301012X

New copper(I) complexes containing the norbornene-substituted phenanthroline ligand were synthesized. Based on these compounds, new carbon-chain copper-containing copolymers possessing the photo- and electroluminescent properties were obtained by the meta

Full text of DOI:10.1134/S107036321301012X

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 1, pp. 72–79. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © Yu.P. Barinova, A.I. Ilicheva, L.N. Bochkarev, V.A. Ilichev, Yu.A. Kurskii, 2013, published in Zhurnal Obshchei Khimii, 2013,
Vol. 83, No. 1, pp. 80–87.
Copper-Containing Copolymers Based
on the Norbornene Monomers. Synthesis, Photo-,
and Electroluminescent Properties
Yu. P. Barinova, A. I. Ilicheva, L. N. Bochkarev, V. A. Ilichev, and Yu. A. Kurskii
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
ul. Tropinina 49, Nizhny Novgorod, 603950 Russia
e-mail: lnb@iomc.ras.ru
Received December 5, 2011
Abstract—New copper(I) complexes containing the norbornene-substituted phenanthroline ligand were
synthesized. Based on these compounds, new carbon-chain copper-containing copolymers possessing the
photo- and electroluminescent properties were obtained by the metathesis polymerization.
DOI: 10.1134/S107036321301012X
To date, there is a significant progress on the
development and practical application of organic light-
emitting diodes (OLEDs) [1, 2]. However, studies
aimed at improving the performance of OLED-devices
permanently develop. One of the challenges in this
area is creating new emitting materials.
In this work we report on the synthesis of new
copper(I) complexes with norbornene-substituted
phenanthroline ligand and of the first electro-
luminescent copper copolymers obtained from them by
the ring-opening metathesis polymerization (ROMP).
The ROMP reactions are widely used for the prepara-
tion of polymers containing a variety of functional
groups in the side chains, including the metal complex
fragments [10, 11]. The same method we used for the
synthesis of copper-containing polymer materials.
Organic and metal-containing polymers are
promising electroluminophores. The significant advan-
tages of polymeric emitters compared with the low-
molecular analogs is that the nanolayers of polymer
emitter can be obtained by the jet printing or spin-
coating, whereas the emission layers of the low-
molecular luminophores are produced by the expensive
high vacuum evaporation. Furthermore, the use of the
polymeric emitters makes possible to produce the
OLED-devices of large area, which is almost unat-
tainable with the low-molecular luminophores.
Recently, the synthesis and efficient photolumine-
scence properties of the copper(I) complex containing
1-ethyl-2-phenyl-1H-imidazo[4,5-f]-1,10-phenanthroline
ligand has been reported [12]. To obtain the same
norbornene-containing copper derivative, capable to
act as a copper-containing monomer, we used two
alternative ways, shown in Fig. 1.
The polymers containing the luminescent metal
complexes are of particular interest, since such light
emitters can generate a variety of colors in almost the
entire range of the visible spectrum.
1-(Bicyclo[2.2.1]hept-5-ene-2-pentyl)-2-phenyl-1H-
imidazo[4,5-f]-1,10-phenanthroline I was used as the
starting reagent in both cases. In the first method, the
initially obtained norbornene-substituted phenanthro-
line ligand II reacts with the acetonitrile copper(I)
complex in the presence of triphenylphosphine or bis
(2-diphenylphosphino)phenyl ether (DPEphos) to the
form the desired copper monomers III and IV. In the
second method in the initial stage the copper
complexes containing ligand I were formed. Then the
hydrogen atom in the imidazole ring of diimine ligand
Recently, the platinum and iridium-containing
polymers have been synthesized and successfully used
as emissive materials in organic light-emitting diodes [3–6].
It is known that a number of the low-molecular
copper(I) complexes has effective electroluminescent
properties [7–9]. Data on the electroluminescent
copper-containing polymers are absent in the literature.
72

COPPER-CONTAINING COPOLYMERS BASED ON THE NORBORNENE MONOMERS
73
Scheme 1.
H
N
N
N
N
I
NaH
[Cu(MeCN)4]BF4 + L
CH2Cl2
DMF
Na
N
H
N
N
N
N
N
LCu
BF4
N
N
NaH
THF
(CH2)5Br
DMF
Na
N
N
N
Cu
L
BF4
(CH2)5
N
N
N
N
N
II
(CH2)5Br
THF
[Cu(MeCN)4]BF4 + L
CH2Cl2
(CH2)5
N
(CH2)5
N
N
N
N
N
LCu
BF4
Cu
L
BF4
N
N
IV (87%)
III (83%)
IV (85%)
III (86%)
L = 2 PPh3 (III), DPEphos (IV).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

74
BARINOVA et al.
Scheme 2.
n
m
+
(CH2)5
(CH2)5
N
N
N
N
N
CuL
BF4
DPEphos (P2).
L = 2 PPh3 (P1),
N
N
Cl
Cl
m
Ru
n
Ph
N
N
(CH2)5
(CH2)5
N
Br
Br
N
N
N
CuL BF4
CH2Cl2
N
P1 (92%)
P2 (95%)
bound to the copper is replaced by a norbornene
absorption spectra of the copper-containing monomers
III, IV and polymer products P1, P2 (Fig. 1, Table 2)
are similar and contain the absorption bands in the
range of 250–325 nm attrubuted to the π→π*-
transitions in the aromatic systems of phosphine and
substituted phenanthroline ligands. Similar to the
spectra of known copper complexes with phenan-
throline ligands [8, 12], the broad bands of lower
intensity in the range of 325–400 nm may be assigned
to the metal-to-ligand charge transfer (MLCT).
The photoluminescence spectra of monomers III,
IV and copolymers P1, P2 (Fig. 2, Table 2) in thin
films contain the broad bands at 520–560 nm related to
the MLCT transitions. In the spectra of copolymers
there are also the high energy excimers of carbazole
groups (375–380 nm) [13], indicating the incomplete
transfer of excitation energy from the polymer matrix
to the luminophore copper complexes.
moiety. As a result, complexes III and IV form.
Compounds III and IV were isolated as the air-
stable yellow solids. NMR spectroscopy revealed that
the complexes are a mixture of endo- and exo-isomers
(80:20).
9-{5-(Bicyclo[2.2.1]hept-5-en-2-yl-pentyl)}-9H-car-
bazole was used as a comonomer to obtain the copper-
containing copolymer, since the carbazole groups in
the polymer emitters improve their charge-transporting
properties and electroluminescent characteristics [2].
Copolymerization proceeds in the presence of Grubbs’
third generation catalyst at room temperature and
results in the target copper copolymers in high yields.
The ratio of carbazole- and copper-containing mono-
mers n:m equals 18:1. The amount of catalyst was 1.0
mol% relative to the total amount of the monomers.
According to the TLC monitoring, the copolymerize-
tion completed within 6 h. The isolated copolymers
(Table 1) are air-stable yellow solids, which are well
soluble in THF, CH2Cl2, and CHCl3.
To study the electroluminescent properties of the
synthesized copolymers, we fabricated the copper-
containing three-layer model OLED-devices of ITO/
Cu-copolymer/BATH/Alq3/Yb configuration, in which
a layer of the indium oxide doped tin oxide (ITO)
served as the anode. The emissive layer consists of the
The study of the photophysical properties of the
copolymers obtained showed that the electron
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COPPER-CONTAINING COPOLYMERS BASED ON THE NORBORNENE MONOMERS
(a)
75
Wavelength, nm
Wavelength, nm
Fig. 2. Photoluminescence spectra (thin films) of com-
pounds III (1), IV (2), P1 (3), P2 (4), λex 350 nm.
(b)
(P2), corresponding to the MLCT transitions in
polymer copper complexes. The absence of emission
of the polymer matrix evidences the effective transfer
of the excitation energy from the carbazole fragments
to the copper-containing luminescent centers by the
Förster mechanism [14]. The emission band in the
electroluminescence spectra of the copolymer P2
containing the DPEphos ligand at the copper atom is
shifted to the long-wave region by 35 nm compared to
the emission of the copolymer P1, containing the
luminophore copper complexes with the PPh3 ligands.
A similar shift of the emission band was observed in
the electroluminescence spectra of the low molecular
weight copper complexes with PPh3 and DPEphos
ligands [7]. OLEDs based on the copolymers P1 and
P2 showed a low brightness [8 cd m–2 at 19 V (P1) and
9 cd m–2 at 20 V (P2)]. This is probably due to the fact
that the relaxation of the excited states of copper
complexes in the electroluminescence occurs largely
Wavelength, nm
Fig. 1. Absorption spectra of the complexes (a) III, IV and
(b) copolymers P1, P2 in CH2Cl2. (1) III, Р1; (2) IV, P2.
copolymer P1 or P2. 4,7-Diphenyl-1,10-phenan-
throline (BATH) and aluminum tris-(8-hydroxy-
quinolate) (Alq3) were used as a hole-blocking and
electron-transporting
layers,
respectively.
The
ytterbium metal layer served as the cathode. The
electro-luminescence spectra of the copolymers P1 and
P2, as well as the performance characteristics of the
OLED-based devices are shown in Figs 3 and 4.
Table 2. Photophysical characteristics of compounds III,
IV, P1, and P2
In the electroluminescence spectra there are the
broad bands with maxima at 525 (P1) and 560 nm
abs
λ
, nm
λmaexm, nm
(film)
max
Compound
(ε×10–5 l mol–1 cm–1), CH2Cl2
275 (0.80), 300 (sh, 0.33), 318 (sh,
0.10), 338 (0.21), 420 (sh, 0.008)
530
III
Table 1. Molecular-mass characteristics and degradation
temperature of copolymers P1, P2
280 (0.39), 302 (sh, 0.19), 318 (sh,
0.10), 337(0.12), 420 (sh, 0.02)
560
IV
P1
P2
–
–
–
–
Copolymer
Td, °C a
293
Mw
Mn
Mw/Mn
1.60
267 (4.70), 284 (3.00), 296 (3.26),
319 (sh, 1.03), 335 (1.43), 347 (1.53)
375, 520
375, 525
P1
P2
33460
20950
23200
12170
1.91
338
265 (4.28), 285 (1.97), 296 (2.88),
320 (sh, 0.55), 333 (0.79), 347 (0.89)
a Temperature at 5% mass loss.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

76
BARINOVA et al.
(a)
Wavelength, nm
Fig. 3. Electroluminescence spectra of ITO/Cu-copolymer/
BATH/Alq3/Yb OLEDs at the maximal brigthness.
Voltage, V
(b)
by non-radiative way. The current-voltage and and bright-
ness-voltage relations (Fig. 4) are typical for OLEDs.
Thus, new copper(I) complexes with the
norbornene-containing phenanthroline ligands were
synthesized. Based on these complexes, we obtained
via the ROMP method previously unknown carbon-
chain copolymers containing in the side chains
luminophore copper complexes and hole-transporting
carbazole fragments. All the compounds are lumine-
scent. In the photoluminescence spectra of the copper-
containing copolymers, there are the emission bands of
carbazole groups excimers (375 nm) and the band at
520–525 nm corresponding to the MLCT transitions in
the copper complexes. The electroluminescence
spectra of copolymers contain only the bands (525 and
560 nm) of the MLCT transitions in the copper
complexes. The maximal brightness of the non-
optimized OLED-devices based on the copper
copolymers is 8–9 cd m–2 at 19.5–20 V. Obviously, the
polymer emitters can be improved by changing the
ligand environment in the luminophore copper
complexes, as well as by optimizing the ratio of the
charge-transporting and luminescent units.
Voltage, V
Fig. 4. (a) The current-voltage and (b) the current-
luminance characteristics of the OLEDs based on the (1) P1
and (2) P2 copolymers.
[20, 21] were synthesized as previously described.
Triphenylphosphine (PPh3), bis(2-diphenylphosphino)-
phenyl ether (DPEphos), aluminum tris(8-hydroxy-
quinolate) (Alq3) and 4,7-diphenyl-1,10-phenan-
throline (BATH), (Aldrich) were used without further
purification.
The H and 13C–{1H} NMR spectra were obtained
1
EXPERIMENTAL
on a Bruker DPX-200 [200 MHz (1H), 50 MHz (13C)]
and Bruker Avance III-400 [400 MHz (1H), 100 MHz
(13C)] spectrometers, internal reference tetra-
methylsilane. The IR spectra were taken on a FSM
1201 FTIR spectrometer from KBr pellets (II, III, IV)
or thin films between the KBr plates (copolymer
samples). The electron absorption spectra were re-
corded on a Perkin Elmer Lambda 25 UV/Vis spectro-
meter. The photoluminescence spectra were obtained
All operations with the easily oxidizable and
hydrolysable substances were carried out in a vacuum
or under argon using standard Schlenk techniques.
Ligand I [15, 16], [Cu(MeCN)4]BF4 [17], bicyclo
[2.2.1]hept-5-en-2-ylpentylbromide
[NBE(CH2)5Br]
[18], 9-{5-(bicyclo[2.2.1]hept-5-en-2-ylpentyl)}-9H-
carbazole [NBE(CH2)5carb] [19], (H2IMes)(3-Br-py)2·
(Cl)2Ru=CHPh (Grubbs’ catalyst of III generation)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

COPPER-CONTAINING COPOLYMERS BASED ON THE NORBORNENE MONOMERS
77
on a Perkin Elmer LS 55 photoluminescence spectro-
meter.
t (2Н), 2.70 m (2Н), 1.90 m (11Н), 1.30–1.15 m (1Н),
0.42–0.36 m (1Н). 13С NMR spectrum (CDCl3), δC,
ppm: 153.96, 148.96, 147.70, 144.83, 144.25, 137.07,
136.78, 132.18, 130.43, 130.38, 129.92, 129.89,
128.93, 128.12, 124.80, 124.19, 123.53, 122.57,
120.13, 49.55, 46.84, 45.33, 42.45, 38.57, 34.39,
32.30, 30.13, 27.90, 26.49. Found, %: С 81.34; Н 6.52.
С31Н30N4. Calculated,%: С 81.22; Н 6.55.
The molecular mass distribution of polymers was
determined by the gel permeation chromatography
(GPC) on a Knauer chromatograph equipped with a
Smartline RID 2300 differential refractometer as a
detector with a set of two Phenomenex columns filled
with Phenogel sorbent (the pore size 104 and 105 Å,
eluent THF, 2 ml min–1, 40°C). The columns were
calibrated using 13 polystyrene standards.
A mixture of [Cu(MeCN)4]BF4 (0.2 g, 0.6 mmol)
and PPh3 (0.34 g, 1.2 mmol) in 10 ml of CH2Cl2 was
stirred for 1 h at room temperature. To the reaction
mixture was added compound II (0.18 g, 0.6 mmol) in
10 ml of CH2Cl2. The mixture was stirred for 2 h at
room temperature. After the removal of solvent and
volatile products the residue was washed with hexane
and dried in a vacuum. The complex III was obtained
(0.62 g, 86%) as a microcrystalline yellow solid, mp
202–205°C. IR spectrum, ν, cm–1: 3050 m (=С–Н,
С–НAr), 1585 w, 1572 w (C–N), 1547 w, 1435 s, 1403
w (СAr–СAr), 1261 w, 1180 w, 1158 w, 810 w, 747 s,
The uncorrected melting points of the monomers
were determined in evacuated sealed capillaries.
Thermal gravimetric analysis (TGA) of the copolymers
was made by a Perkin Elmer PYRIS 6 TGA thermo-
gravimeter in a stream of dry nitrogen (the flow rate
80 cm3 min–1, the heating rate 5°C min–1).
The electroluminescence spectra, current-voltage
and voltage-brightness characteristics were obtained
for the model OLED-devices without encapsulation
using an automated PC-coupled complex, including a
GW INSTEK PPE-3323 power supply, GW INSTEK
GDM-8246 digital multimeter and Ocean Optics USB
2000 spectrofluorimeter.
1
694 s. H NMR spectrum (CDCl3), δ, ppm: 9.26 br. s
(2H), 8.46 br. s (4Н), 7.69–7.54 m (5Н), 7.31 t (9Н),
7.15 m (11Н), 7.08 m (10Н), 6.10 d.d (0.8 Нendo), 6.02
m (0.4 Нexo) 5.91 d.d (0.8 Нendo), 3.40 m (2Н), 2.74 m
(2Н), 1.84 m (3Н), 1.43–1.03 m (10Н). 13С NMR
spectrum (CDCl3), δC, ppm: 145.07, 140.60, 137.00,
133.21, 132.32, 132.02, 131.58, 129.90, 129.02,
128.71, 128.07, 127.56, 123.51, 49.60, 45.54, 38.68,
36.37, 34.57, 34.00, 32.85, 32.43, 28.42, 27.28. Found,
%: С 71.09; Н 5.32. С67Н60BCuF4N4P2. Calculated, %:
С 70.96; Н 5.29.
1-{5-(Bicyclo[2.2.1]hept-5-en-2-ylpentyl)}-2-phe-
nyl-1Н-imidazo[4,5-f]-1,10-phenanthrolinobis(tri-
phenylphosphine)copper tetrafluoroborate (III). a.
To a solution of compound I (0.82 g, 2.8 mmol) in
30 ml of DMF was added in small portions 0.10 g of
NaH (4.0 mmol). When the hydrogen evolution ceased,
the reaction mixture was stirred for 2 h at 80°C. To the
resulting solution was added NBE(CH2)5Br (0.81 g,
3.3 mmol). The mixture was stirred for 12 h at 80°C.
After cooling to room temperature, the reaction
mixture was poured into 100 ml of distilled water. The
products were extracted with chloroform (3×50 ml).
The combined extracts were washed with distilled
water (3×50 ml) and dried with anhydrous magnesium
sulfate. The solvent was removed by evaporation in a
vacuum; the residue was recrystallized from ethanol.
1-{5-(Bicyclo[2.2.1]hept-5-en-2-ylpentyl)}-2-phenyl-
1Н-imidazo[4,5-f]-1,10-phenanthroline (II) was
obtained in 44% (0.55 g) yield as the microcrystalline
colorless substance, mp 176–178°C. IR spectrum, ν,
cm–1: 3053 w (=С–Н, С–НAr), 1562 w, 1550 w (C–N),
1513 w, 1400 w (СAr–СAr), 1260 w, 1180 w, 1158 w,
b. A mixture of [Cu(MeCN)4]BF4 (0.14 g, 0.44 mmol)
and PPh3 (0.23 g, 0.88 mmol) in 10 ml of CH2Cl2 was
stirred for 1 h at room temperature. To this solution
was added compound I (0.13 g, 0.44 mmol) in 10 ml
of CH2Cl2 and the mixture was stirred for 2 h at room
temperature. The solvent and volatiles were removed
by evaporation in a vacuum. To a solution of the
resulting complex [(PPh3)2Cu(I)]BF4 [22] in 10 ml of
THF was added in small portions NaH (0.011 g,
0.44 mmol). The reaction mixture was stirred for 2 h at
room temperature. Then to the resulting mixture was
added NBE(CH2)5Br (0.11 g, 0.45 mmol) in 5 ml of
THF. The mixture was stirred for 18 h at room
temperature. The precipitated NaBr was separated by
centrifugation. After the solvent removal, the residue
was washed with hexane and dried in a vacuum. Yield
0.42 g (83%). The IR and NMR spectral data are
identical to those of compound III obtained by the
method mentioned above.
1
810 m, 777 w, 741 m, 702 m. H NMR spectrum
(CDCl3), δ, ppm: 9.47 m (2Н), 9.06 d.d (1Н), 8.55 d.d
(1Н), 7.73–7.66 m (4Н), 7.59–7.56 m (3Н), 6.05 d.d
(0.8 Нendo), 6.02 m (0.4 Нexo), 5.80 d.d (0.8 Нendo), 4.58
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013

78
BARINOVA et al.
1-(5-Bicyclo[2.2.1]hept-5-en-2-ylpentyl)-2-phenyl-
decompose the catalyst. The reaction mixture was
stirred for an additional 30 min. The resulting polymer
was precipitated with hexane followed by repre-
cipitation with hexane from CH2Cl2 and drying in a
vacuum at room temperature to a constant weight. The
copolymer P1 was obtained as a pale yellow solid in
92% yield (0.22 g). IR spectrum, ν, cm–1: 2930 s, 2855
m (CAr–Н), 1627 w, 1598 m, 1482 s, 1452 s (СAr–СAr),
1346 m, 1325 s (С–N), 1263 m, 1231 m, 1154 m, 971
w, 748 s, 725 s, 618 w. 1H NMR spectrum (CDCl3), δ,
ppm: 8.05 d (22Н), 7.36–7.17 m (192Н), 5.20–5.14 m
(25Н), 4.19–4.06 m (20Н), 2.68 m (10Н), 2.17 m
(18Н), 1.76 m (101Н), 1.26–1.00 m (158Н). Found, %:
С 84.80; Н 7.70. С499Н546BCuF4N22P2. Calculated, %:
С 84.87; Н 7.74.
1Н-imidazo[4,5-f]-1,10-phenanthrolino[bis(2-diphenyl-
phosphino)phenyl ether]copper tetrafluoroborate
(IV). а. Synthesis of compound IV was similar to that
of the complex III. Yield 0.64 g (87%), micro-
crystalline yellow solid, mp 260–265°C (decomp.). IR
spectrum, ν, cm–1: 3050 w (=С–Н, С–НAr), 1586 w,
1572 w (C–N), 1547 w, 1477 w, 1402 w (СAr–СAr),
1308 w, 1260 m, 1183 m (C–H), 1158 w, 810 m, 744
1
m, 697 m. H NMR spectrum (CDCl3), δ, ppm: 9.17 d
(2Н), 8.57 d (2Н), 8.34 d (2Н), 7.45–7.39 m (5Н), 7.07
t (14Н), 7.00–6.94 m (14Н), 6.10 d.d (0.8 Нendo), 6.02
m (0.4 Нexo) 5.91 d.d (0.8 Нendo), 3.74 (1Н), 3.40 t
(1Н), 2.74 m (2Н), 1.85 m (3Н), 1.43–1.05 m (10Н).
13С NMR spectrum (CDCl3), δС, ppm: 146.67, 137.00,
134.39, 133.23, 133.06, 132.90, 131.67, 131.50,
131.17, 130.83, 129.90, 128.64, 128.55, 128.45,
128.37, 126.95, 124.96, 123.29, 120.31, 49.59, 45.42,
42.54, 36.67, 34.57, 33.99, 32.42, 30.11, 28.42, 27.78,
25.63. Found, %: С 70.16; Н 5.11. С67Н58B·
CuF4N4OP2. Calculated, %: С 70.10; H 5.06.
Copolymerization of the monomer IV (0.04 g,
0.035 mmol) and NBE(CH2)5carb (0.2 g, 0.62 mmol)
was carried out similarly at room temperature for 6 h.
The copolymer P2 was obtained as a pale yellow solid
in 95% yield (0.23 g). IR spectrum, ν, cm–1: 1482 s,
1461 s, 1452 s (СAr–СAr), 1346 m, 1325 s (С–N), 263
1
b. A mixture of [Cu(MeCN)4]BF4 (0.14 g, 0.44 mmol)
and DPEphos (0.24 g, 0.44 mmol) in 10 ml of CH2Cl2
was stirred for 1 h at room temperature. To this
solution was added compound I (0.13 g, 0.44 mmol) in
10 ml of CH2Cl2, and the mixture was stirred for 2 h at
room temperature. The solvent and volatiles were
removed by evaporation in a vacuum. The resulting
complex [(DPEphos)Cu(I)]BF4 [23] was dissolved in
10 ml of THF. To this solution was added in small
portions NaH (0.011 g, 0.44 mmol). The reaction
mixture was stirred for 2 h at room temperature. Then,
to the resulting solution was added NBE(CH2)5Br
(0.11 g, 0.45 mmol) in 5 ml of THF, and the mixture
was stirred for 18 h at room temperature. The
precipitated NaBr was separated by centrifugation.
After the solvent removal, the residue was washed
with hexane and dried in a vacuum. Yield 0.43 g
(85%). The IR and NMR spectral data are identical to
those of compound IV obtained by the method
mentioned above.
m, 1231 m, 1154 m, 971 w, 748 s, 725 s, 618 w. H
NMR spectrum (CDCl3), δ, ppm: 8.05 d (24Н), 7.35–
7.17 m (171Н), 5.23–5.17 m (29Н), 4.18 m (24 Н),
2.75 m (13Н), 2.39 m (9Н), 1.80–1.59 m (122Н),
1.26–1.00 m (152Н). Found, %: С 84.76; Н 7.56.
С499Н544BCuF4N22ОP2. Calculated, %: С 84.71; Н 7.69.
OLED-Devices fabrication. A glass ITO-coated
(120 nm, 15 Ω cm–2, Lum Tec) plate, which acts as the
anode, was used as a support for the OLED-devices of
ITO/Cu-copolymer (40 nm)/BATH (30 nm)/Alq3
(30 nm)/Yb (150 nm) configuration. The emission
layer of the copolymer was deposited from its CH2Cl2
solution (5 mg ml–1) using a Spincoat G3-8 centrifuge
(3000 rev min–1, 30 s) and dried in a vacuum at 70°C
for 3 h. The layer thickness was determined by a
META-900 ellipsometer. A hole-blocking layer of
BATH, the electron-transporting layer Alq3 and a Yb
layer (Aldrich), which plays a cathode role, was
deposited by evaporation in a vacuum (10–6 mm Hg)
from the heat-resisting evaporators. The layer
thickness was monitored by a calibrated quartz
resonator. The active area of the device is a circle with
a diameter of 5 mm.
Synthesis of copolymers P1, P2. To a solution of
the monomer III (0.04 g, 0.034 mmol) and NBE·
(CH2)5carb (0.2 g, 0.62 mmol) in 5 ml of CH2Cl2 was
added a solution of the Grubbs’ catalyst of III
generation (0.006 g, 0.0067 mmol) in 1 ml of CH2Cl2.
The mixture was stirred at room temperature. The
polymerization process was monitored by TLC. After
the reaction completed (6 h), to the reaction mixture
was added a few drops of ethyl vinyl ether to
ACKNOWLEDGMENTS
This work was supported by the Russian
Foundation for Basic Research (project no 11-03-
97021 r_povolzhe_a). The authors thank M.A. Lopatin
for obtaining the absorption and photoluminescence
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