Pyrrolo[3,2-b]pyrrole-Based Copolymers Bull. Korean Chem. Soc. 2013, Vol. 34, No.

11 3399
http://dx.doi.org/10.5012/bkcs.2013.34.11.3399
Pyrrolo[3,2-b]pyrrole-Based Copolymers as Donor Materials for
Organic Photovoltaics
Suhee Song, Seo-Jin Ko,

Hyunmin Shin, Youngeup Jin,

Il Kim,

Jin Young Kim,

Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology,
Ulsan 689-798, Korea.
*
E-mail: [email protected]

Department of Industrial Chemistry, Pukyong National University, Busan 608-739, Korea

The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science
and Engineering, Pusan National University, Busan 609-735, Korea
Received June 7, 2013, Accepted August 30, 2013
A new accepter unit, pyrrolo[3,2-b]pyrrole-2,5-dione, was prepared and utilized for the synthesis of the
conjugated polymers containing electron donor-acceptor pair for OPVs. Pyrrolo[3,2-b]pyrrole-2,5-dione unit,
regioisomer of the known pyrrolo[3,4-c]pyrrole-1,4-dione, is originated from the structure of stable synthetic
pigment. The new conjugated polymers with 1,4-diphenylpyrrolo[3,2-b]pyrrole-2,5-dione, thiophene and
carbazole were synthesized using Suzuki polymerization to generate P1 and P2. The solid films of P1 and P2
show absorption bands with maximum peaks at about 377, 554 and 374, 542 nm and the absorption onsets at
670 and 674 nm, corresponding to band gaps of 1.85 and 1.84 eV, respectively. To improve the hole mobility
of the polymer with 1,4-bis(4-butylphenyl)-pyrrolo[3,2-b]-pyrrole-2,5-dione unit, which was previously
reported by us, the butyl group at the 4-positions of the N-substituted phenyl group was substituted with
hydrogen and methyl group. The field-effect hole mobility of P2 is 9.6 10
5
cm
2
/Vs. The device with
P2:PC
71
BM (1:2) showed V
OC
value of 0.84 V, J
SC
value of 5.10 mA/cm
2
, and FF of 0.33, giving PCE of 1.42%.
Key Words : Polymer-based solar cells, Photovoltaic cells, Pyrrolo[3,2-b]pyrrole-2,5-dione
Introduction
In recent years, the development of efficient polymer-
based solar cells has become an active area of research due
to their potential as alternative source of green energy.
1-3
Organic photovoltaics (OPVs) with bulk heterojunction
(BHJ) architecture have attracted substantial attentions due
to its possibility to be renewable clean energy for low-cost,
lightweight, printable, and flexible large area devices.
4,5
Conjugated polymers as the donor with the fullerene derivative
PCBM as the acceptor have achieved impressive values of
power conversion efficiency (PCE) near 8%
6
to 10%
7
in
bulk heterojunction (BHJ) devices.
6,7

To obtain low bandgap conjugated polymers with planar
molecular geometries, various types of aromatic heterocycles
have been widely investigated in OPVs.
8-10
Semiconducting
copolymers with diketopyrrolopyrrole units are emerging as
interesting materials for optoelectronic applications in field-
effect transistors (FETs)
11
and organic photovoltaic cells.
12
The pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) chromophore has
been primarily known in commercial high-performance
pigments with heat stability and high and balanced hole and
electron mobilities for optoelectronic applications. The DPP
unit constitutes a planar moiety capable of providing -
stacking in the solid state to generate efficient charge
transport.
13
The pyrrolo[3,2-b]pyrrole-2,5-dione (iDPP)
exhibiting absorption in the near IR range, the structure of a
natural dye found in lichens,
14
is the regioisomer of the
known DPP which has been used as the electron rich unit.
15
In our previous study, new electron deficient unit, 1,4-bis(4-
butylphenyl)-pyrrolo[3,2-b]-pyrrole-2,5-dione, has been
designed and utilized for the efficient ICT to generate
polymer with low band gap.
16
In this paper, we reported the synthesis and characteri-
zation of polymers with iDPP for OPV device. At the 4-
positions of the N-substituted phenyl groups of 1,4-bis(4-
butylphenyl)-pyrrolo[3,2-b]-pyrrole-2,5-dione unit, the butyl
group was substituted with hydrogen or methyl group to
improve the hole mobility. The low bandgap conjugated
polymers were synthesized by Suzuki coupling reaction of
iDPP as the electron poor unit and carbazole as the electron
rich unit with thiophene as the bridge. The photovoltaic
properties of the polymers were investigated by fabrication
of the polymer solar cells with the configuration of ITO/
PEDOT:PSS/polymer:PCBM/Al.
Results and Discussion
Synthesis and Characterization. The general synthetic
routes of the monomers and polymers are outlined in
Scheme 1. In the first step, ethyl 2-thiopheneacetate (1) was
brominated with N-bromosuccinimide (NBS) to generate
ethyl 2-(5-bromo-2-thienyl)acetate (2). The aniline (3) and
p-toluidine (4) were treated with oxalyl chloride (6) and PCl
5
3400 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 11 Suhee Song et al.
in toluene to provide diphenylethanediimidoyl dichloride (6)
and N,N'-bis(4-methylphenyl)ethanediimidoyl dichloride
(7), respectively. Ethyl 2-(5-bromo-2-thienyl)acetate (2) and
compound 6 (or compound 7) were coupled using
Na[N(SiMe
3
)
2
] to form 3,6-bis{5-[4-(diphenylamino)phen-
yl]-2-thienyl}-1,4-diphenylpyrrolo[3,2-b]pyrrole-2,5-dione
(8) (or 3,6-bis{5-[4-(diphenylamino)phenyl]-2-thienyl}-1,4-
bis(4-methylphenyl)pyrrolo[3,2-b]pyrrole-2,5-dione (9)).
Compound 8 (or compound 9), as electron-accepting moiety,
and 2,7-bis(4',4',5',5'-tetramethyl-1',3',2'-dioxaborolan-2'-
yl)-N-9''-heptadecanylcarbazole (10),
10
as electron-donating
unit, were co-polymerized through Suzuki coupling reaction
with Pd(0)-catalyst to yield poly(N-9-heptadecanyl-2,7-
carbazole-alt-3,6-bis{5-[4-(diphenylamino)phenyl]-2-thien-
yl}-1,4-diphenylpyrrolo[3,2-b]pyrrole-2,5-dione) (P1) (or
poly(N-9-heptadecanyl-2,7-carbazole-alt-3,6-bis{5-[4-(di-
phenylamino)phenyl]-2-thienyl}-1,4-bis(4-methylphenyl)-
pyrrolo[3,2-b] pyrrole-2,5-dione) (P2)). The structures and
purities of the monomers were confirmed by
1
H-NMR,
13
C-
NMR, and HRMS. The synthesized polymers were soluble
in various organic solvents such as chloroform, chloroben-
zene, tetrahydrofuran (THF), dichloromethane and o-di-
chlorobenzene (ODCB).
Table 1 summarizes the polymerization results including
molecular weight, polydispersity index (PDI) and thermal
stability of the polymers. The weight-average molecular
weight (M
w
) of 16700 and 32800 with polydispersity index
(PDI, M
w
/M
n
) value of 3.0 and 2.4 of the P1 and P2 were
determined by gel permission chromatography (GPC), respec-
tively. The thermal properties of the polymers were charac-
terized by both differential scanning calorimetry (DSC) and
thermal gravimetric analysis (TGA). TGA was performed
with TGA 2950 in a nitrogen atmosphere at a heating rate of
10 C/min to 600 C. The DSC analysis was performed
under a nitrogen atmosphere (50 mL/min) on a DSC 2920 at
heating rate of 10 C/min. The decomposition temperatures
(T
d
, 5% weight loss) are 407 and 388
o
C for P1 and P2 under
Scheme 1. Synthetic route for the synthesis of the monomer and
polymer.
Table 1. Polymerization Result and Properties of Polymer
Polymer Mn
a
Mw
a
PDI
a
DSC (Tg) TGA (Td)
b
max (sol.) max (film)
P1 5500 16700 3.0 116 407 352, 540 377, 554
P2 13600 32800 2.4 95 388 367, 541 374, 542
a
Molecular weight (Mw) and polydispersity (PDI) of the polymers were determined by gel permeation chromatography (GPC) in THF using polystyrene
standards.
b
Onset decomposition temperature (5% weight loss) measured by TGA under N2.
Figure 1. UV-visible absorption spectra of polymer in chloroform
solution and the solid state.
Pyrrolo[3,2-b]pyrrole-Based Copolymers Bull. Korean Chem. Soc. 2013, Vol. 34, No. 11 3401
N
2
. The T
d
value of P1 is higher than that of P2 with two
methyl groups introduced at 4-positions of the N-substituted
phenyl groups. The P1 and P2 showed good thermal
stability with glass transition temperature (T
g
) values of 116
and 95
o
C, using DSC performed at a temperature range of
30 to 200
o
C. The T
g
value of P1 is higher than that of P2
caused by crystallinity coming from the removal of the
methyl groups. The high thermal stability of the resulting
polymers prevents the deformation of the polymer morpho-
logy and is important for organic photovoltaics (OPVs)
application.
Optical Properties. The optical properties of chloroform
solution and films of the polymers were investigated by UV-
vis absorption spectroscopy as shown in Figure 1. Uniform
films were prepared on quartz plate by spin-casting from
their chloroform solution at room temperature. The
absorption spectra of P1 and P2 exhibited maximum peaks
at about 352, 540 and 367, 541 nm in solution, respectively.
The short wavelength absorption peak of P1 in solution was
blue shifted about 16 nm as compared with that of the
polymer based on pyrrolo[3,2-b]pyrrole-2,5-dione (iDPP)
with butyl chains (P-Butyl)
16
caused by lower molecular
weight. The solid films of P1 and P2 show absorption bands
with maximum peaks at about 377, 554 and 374, 542 nm
and the absorption onsets at 670 and 674 nm, corresponding
to band gaps of 1.85 and 1.84 eV, respectively. The
absorption peaks of P1 in film were red shifted as compared
with the case of P-Butyl because the alkyl chain, which
prevent -
*
stacking of the polymer backbone, was
removed. In both cases of P1 and P2, the short wavelength
absorption maxima and the absorption onsets of the films
were red shifted as compared to the solution state. The long
wavelength absorption peaks of the films show higher fwhm
(full width at half maximum) as compared to the cases of the
solution state. The short-wavelength absorption peak has
been ascribed to a delocalized excitonic -
*
transition in the
conjugated chain and the long-wavelength absorption peak
attributed to the intramolecular charge transfer (ICT)
between the carbazole and iDPP units.
17
Electrochemical Properties. The electrochemical property
of the polymer was determined from the bandgap estimated
from the absorption onset wavelength, and the HOMO
energy level which was estimated from the cyclic voltam-
metry (CV). The CV was performed with a solution of
tetrabutylammonium tetrafluoroborate (Bu
4
NBF
4
) (0.10 M)
in acetonitrile at a scan rate of 100 mV/s at room temper-
ature under argon atmosphere. A platinum electrode (~0.05
cm
2
) coated with a thin polymer film was used as the work-
ing electrode. Pt wire and Ag/AgNO
3
electrode were used as
the counter electrode and reference electrode, respectively.
The energy level of the Ag/AgNO
3
reference electrode
(calibrated by the Fc/Fc
+
redox system) was 4.8 eV below
the vacuum level.
18
The CV spectra are shown in Figure 2,
and the oxidation potentials derived from the onsets of
electrochemical p-doping are summarized in Table 2. HOMO
and LUMO levels were calculated according to the em-
pirical formula (E
HOMO
= ([E
onset
]
ox
+ 4.8) eV) and (E
LUMO
=
([E
onset
]
red
+ 4.8) eV), respectively. The polymers, P1 and
P2, exhibited the absorption onset wavelengths of 670 and
674 nm in solid thin films, which correspond to band gaps of
1.85 and 1.84 eV, respectively. The polymers exhibit irrever-
sible processes in an oxidation scan. The oxidation onsets of
the P1 and P2 were estimated to be 0.66 and 0.67 V, which
correspond to HOMO energy levels of 5.46 and 5.47 eV,
respectively. The reduction potential onsets of P1 and P2 are
1.26 and 1.15 V, which correspond to LUMO energy
levels of 3.54 and 3.65 eV, respectively. The electro-
chemical bandgaps, calculated from cyclic voltammetry data,
are about 1.92 and 1.82 eV.
FET and Photovoltaic Properties. The field-effect carrier
mobilities of the polymers were measured by fabricating
thin film field-effect transistors (FETs) using the top-contact
geometry. Figure 3 shows the FET transfer characteristics of
the polymer devices of the OTS-modified SiO
2
. Hole
mobilities of the P1 and P2 were calculated from the transfer
characteristics of the OFETs. To improve the hole mobility
of the polymer with 1,4-bis(4-butylphenyl)-pyrrolo[3,2-b]-
pyrrole-2,5-dione unit, which was previously reported by us,
the butyl group at the 4-positions of the N-substituted phenyl
group was substituted with hydrogen and methyl group to
provide P1 and P2. The field-effect hole mobilities of P1
and P2 are 1.6 10
5
and 9.6 10
5
cm
2
/Vs, respectively.
Figure 2. Electrochemical properties of polymers.
Table 2. Electrochemical potentials and energy levels of the polymer
Polymer Optical band gap
a
(eV) HOMO
b
(eV) LUMO
c
(eV) Eox
d
(V) Ered
d
(V) Chemical band gap
e
(eV)
P1 1.85 -5.46 -3.54 0.66 -1.26 1.92
P2 1.84 -5.47 -3.65 0.67 -1.15 1.82
a
Optical energy band gap was estimated from the onset wavelength of the optical absorption.
b
Calculated from the oxidation potentials.
c
Calculated
from the reduction potentials.
d
Onset oxidation and reduction potential measured by cyclic voltammetry.
e
Calculated from the Eox and Ered.
3402 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 11 Suhee Song et al.
Through this modification, the mobility was increased in
case of P2 but was decreased in case of P1 caused by its
relatively poor solubility.
The OPVs were fabricated by spin-casting of ODCB
solution of PCBM/polymers. All polymers were applied as
donors into a conventional BHJ type OPV device with
PC
71
BM as acceptor, which has been widely used for this
purpose. Typical J-V characteristics of devices with the
configuration of ITO/PEDOT:PSS (40 nm)/polymer:PC
71
BM
(1:2) (80 nm)/without or with TiOx (10 nm)/Al (100 nm)
under AM 1.5G irradiation (100 mW/cm
2
) are depicted in
Figure 4. The photovoltaic parameters for all the polymers,
including open circuit voltage (V
OC
), short circuit current
density (J
SC
), fill factor (FF), and power conversion
efficiency (PCE) are summarized in Table 3. The device of
P1:PC
71
BM (1:2) showed V
OC
value of 0.65 V, J
SC
value of
4.23 mA/cm
2
, and FF of 0.34, giving PCE of 0.93%. The
device with P2:PC
71
BM (1:2) showed V
OC
value of 0.84 V,
J
SC
value of 5.10 mA/cm
2
, and FF of 0.33, giving PCE of
1.42%. In case of the devices with blending ratio of 1:2, the
PCE values of the devices were increased caused by the
increased current density. However, neither of the processes,
using 1,8-diiodooctane (DIO) or thermal treatment, improved
the performance in the devices based on the polymer:PCBM
(1:2) blend. The incident photon to current efficiency (IPCE)
spectra of the photovoltaic devices from polymer:PC
71
BM
blends are presented in Figure 5. The IPCE spectra of the
polymers show maxima of 17.3% at 550 nm for P1 and
30.5% at 380 nm for P2.
Conclusions
The polymers, P1 and P2 utilizing the acceptor unit,
diphenylpyrrolo[3,2-b]pyrrole-2,5-dione, were synthesized
to show good solubility at room temperature in organic
solvents. Pyrrolo[3,2-b]pyrrole-2,5-dione unit, regioisomer
of the known pyrrolo[3,4-c]pyrrole-1,4-dione, is originated
from the structure of stable synthetic pigment. The solid
films of P1 and P2 show absorption bands with maximum
peaks at about 377, 554 and 374, 542 nm and the absorption
onsets at 670 and 674 nm, corresponding to band gaps of
1.85 and 1.84 eV, respectively. The hole mobility of P2 is
9.6 10
5
cm
2
/Vs. The device with P2:PC
71
BM (1:2) show-
ed V
OC
value of 0.84 V, J
SC
value of 5.10 mA/cm
2
, and FF of
0.33, giving PCE of 1.42%.
Experimental Section
General. All reagents were purchased from Aldrich or
TCI, and used without further purification. Solvents were
purified by normal procedure and handled under moisture-
Figure 3. Transfer Characteristics of PCDTPPDB-based Top-
contact OFETs.
Figure 4. Current density-potential characteristics of the polymer
solar cell under the illumination of AM 1.5, 100 mW/cm
2
.
Table 3. Photovoltaic properties of the polymer
Polymer
doron:
PCBM
VOC
(V)
JSC
(mA/cm
2
)
FF
PCE
(%)
P1
1:2
a
0.76 3.11 0.37 0.87
1:2
b
0.65 4.23 0.34 0.93
1:3
b
0.66 3.58 0.36 0.85
1:4
b
0.65 3.92 0.33 0.86
P2
1:2
a
0.84 3.84 0.33 1.06
1:2
b
0.84 5.10 0.33 1.42
1:3
b
0.81 3.00 0.31 0.75
1:4
b
0.82 2.30 0.31 0.58
a
using PC61BM.
b
using PC71BM.
Figure 5. IPCE curve of the polymer solar cells under the
illumination of AM 1.5, 100 mW/cm
2
.
Pyrrolo[3,2-b]pyrrole-Based Copolymers Bull. Korean Chem. Soc. 2013, Vol. 34, No. 11 3403
free atmosphere.
1
H and
13
C NMR spectra were recorded
with a Varian Gemini-300 (300 MHz) spectrometer and
chemical shifts were recorded in ppm units with TMS as the
internal standard. Flash column chromatography was per-
formed with Merck silica gel 60 (particle size 230-400 mesh
ASTM) with ethyl acetate/hexane or methanol/methylene
chloride gradients unless otherwise indicated. Analytical
thin layer chromatography (TLC) was conducted using
Merck 0.25 mm silica gel 60F pre-coated aluminum plates
with fluorescent indicator UV254. High resolution mass
spectra (HRMS) were recorded on a JEOL JMS-700 mass
spectrometer under electron impact (EI) conditions in the
Korea Basic Science Institute (Daegu). The UV-vis absorption
spectra were recorded by a Varian 5E UV/VIS/NIR spectro-
photometer, while the Oriel InstaSpec IV CCD detection
system with xenon lamp was used for the photoluminescence
and electroluminescence spectra measurements.
Solar cells were fabricated on an indium tin oxide (ITO)-
coated glass substrate with the following structure; ITO-
coated glass substrate/poly(3,4-ethylenedioxythiophene)
(PEDOT:PSS)/small molecule: PCBM/Al. The ITO-coated
glass substrate was first cleaned with detergent, ultrasoni-
cated in acetone and isopropyl alcohol, and subsequently
dried overnight in an oven. PEDOT:PSS (Baytron PH) was
spin-cast from aqueous solution to form a film of 40 nm
thickness. The substrate was dried for 10 min at 140 C in
air and then transferred into a glove box to spin-cast the
active layer. A solution containing a mixture of small mole-
cule:PCBM in dichlorobenzene solvent with concentration
of 7 wt %/mL was then spin-cast on top of the PEDOT/PSS
layer. The film was dried for 60 min at 70 C in the glove
box. The sample was heated at 80
o
C for 10 min in air. Then,
an aluminum (Al, 100 nm) electrode was deposited by
thermal evaporation in a vacuum of about 5 10
7
Torr.
Current density-voltage (J-V) characteristics of the devices
were measured using a Keithley 236 Source Measure Unit.
Solar cell performance utilized an Air Mass 1.5 Global (AM
1.5 G) solar simulator with an irradiation intensity of 1000
W m
2
. An aperture (12.7 mm
2
) was used on top of the cell to
eliminate extrinsic effects such as cross-talk, waveguiding,
shadow effects, etc. The spectral mismatch factor was
calculated by comparison of solar simulator spectrum with
AM 1.5 spectrum at room temperature. The IPCE is a
measure of the photon to electron conversion efficiency at a
particular irradiation wavelength (Eq. 1).
IPCE = (1240 J
SC
) / (
i
P
in
) (1)
Synthesis of Ethyl 2-(5-bromo-2-thienyl)acetate (2): Ethyl
2-thiopheneacetate (1) (10 g, 66.66 mmol) was brominated
with N-bromosuccinimide (NBS) (13 g, 73.26 mmol) in
THF (20 mL) at room temperature. After stirring for 24 h,
water (200 mL) and ethyl acetate (400 mL) were added. The
organic layer was washed with 3 200 mL of water and
concentrated under reduced pressure. The residue was
purified by flash column chromatography to give compound
2 as a yellow oil;
1
H NMR (300 MHz, CDCl
3
) 1.29 (t, 3H,
J = 7.1 Hz), 3.76 (s, 2H), 4.19 (q, 2H, J = 7.1 Hz ), 6.69
(d, 1H, J = 3.8 Hz), 6.90 (d, 1H, J = 3.8 Hz);
13
C NMR (75
MHz, CDCl
3
) 14.35, 36.07, 61.59, 111.55, 127.31, 129.66,
137.09, 170.05; HRMS (EI
+
, m/z)

calcd for C
8
H
9
BrO
2
S
247.9507, measured 247.9509.
Synthesis of Diphenylethanediimidoyl Dichloride (6):
A solution of aniline (3) (54.82 mmol) and oxalyl chloride
(5) (10.9 mL, 115 mmol) in toluene (50 mL) was treated
with PCl
5
(12.53 g, 60 mmol) at room temperature. After
stirring for 30 min, the reaction mixture was heated at 100
o
C until no further hydrogen chloride was formed. The
reaction mixture was concentrated under reduced pressure
and crude product was recrystallized from hexane/CH
2
Cl
2
to
afford compound 6 as a yellow crystal. mp 100
o
C;
1
H NMR
(300 MHz, CDCl
3
) 7.12 (d, 4H, J = 8.5 Hz), 7.29 (t, 2H, J
= 6.8 Hz), 7.47 (t, 4H, J = 7.2 Hz);
13
C NMR (75 MHz,
CDCl
3
) 120.67, 126.91, 129.28, 138.89, 146.03; HRMS
(EI
+
, m/z)

calcd for C
14
H
10
Cl
2
N
2
276.0221, measured 276.0221.
Synthesis of N,N'-Bis(4-methylphenyl)ethanediimidoyl
Dichloride (7): A solution of p-toluidine (4) (46.24 mmol)
and oxalyl chloride (5) (9.3 mL, 98 mmol) in toluene (50
mL) was treated with PCl
5
(11 g, 52 mmol) at room temper-
ature. After stirring for 30 min, the reaction mixture was
heated at 100
o
C until no further hydrogen chloride was
formed. The reaction mixture was concentrated under reduced
pressure and crude product was recrystallized from hexane/
CH
2
Cl
2
to afford compound 7 as a yellow crystal. mp 100
o
C;
1
H NMR (300 MHz, CDCl
3
) 2.40 (s, 6H), 7.08 (d, 4H,
J = 8.0 Hz), 7.26 (d, 4H, J = 7.7 Hz);
13
C NMR (75 MHz,
CDCl
3
) 21.42, 121.09, 129.79, 137.05, 138.07, 143.31;
HRMS (EI
+
, m/z)

calcd for C
16
H
14
Cl
2
N
2
304.0534, measured
304.0531.
Synthesis of 3,6-Bis(5-(4-(diphenylamino)phenyl)-2-
thienyl)-1,4-diphenylpyrrolo[3,2-b]pyrrole-2,5-dione (8):
Ester 2 (33.23 mmol) and 1 M NaN(SiMe
3
)
2
(144 mmol)
was dissolved in THF (30 mL) at room temperature under
argon. After stirring for 1 h, the reaction mixture was cooled
to 78 C and a THF solution (30 mL) of the compound 6
(15.75 mmol) was slowly added. After stirring for 48 h at
room temperature, aqueous solution of NH
4
Cl (5 M, 250
mL) and ethyl acetate (400 mL) were added. The organic
layer was washed with 3 200 mL of water and concentrated
under reduced pressure. The residue was purified by flash
column chromatography to give compound 8 as a red solid.
mp 300
o
C;
1
H NMR (300 MHz, CDCl
3
) 5.95 (d, 2H, J =
4.1 Hz), 6.71 (d, 2H, J = 3.8 Hz), 7.30-7.32 (m, 4H),
7.45-7.48 (m, 6H);
13
C NMR not obtained due to the low
solubility; HRMS (EI
+
, m/z)

calcd for C
26
H
14
Br
2
N
2
O
2
S
2
607.8863, measured 607.8865.
Synthesis of 3,6-Bis(5-(4-(diphenylamino)phenyl)-2-thienyl)-
1,4-bis(4-methylphenyl)pyrrolo[3,2-b]pyrrole-2,5-dione (9):
Ester 2 (23.12 mmol) and 1 M NaN(SiMe
3
)
2
(98 mmol) was
dissolved in THF (30 mL) at room temperature under argon.
After stirring for 1 h, the reaction mixture was cooled to 78 C
and a THF solution (30 mL) of the compound 7 (10.56
mmol) was slowly added. After stirring for 48 h at room
temperature, aqueous solution of NH
4
Cl (5 M, 250 mL) and
ethyl acetate (400 mL) were added. The organic layer was
3404 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 11 Suhee Song et al.
washed with 3 200 mL of water and concentrated under
reduced pressure. The residue was purified by flash column
chromatography to give compound 9 as a red solid. mp 300
o
C;
1
H NMR (300 MHz, CDCl
3
) 2.44 (s, 6H), 5.99 (d, 2H,
J = 4.1 Hz), 6.72 (d, 2H, J = 4.1 Hz), 7.18 (d, 4H, J = 8.5
Hz), 7.26 (d, 4H, J = 6.3 Hz);
13
C NMR (500 MHz,
CDCl
3
) 21.25, 100.18, 109.99, 110.00, 116.33, 126.97,
129.44, 129.79, 129.88, 130.75, 131.16, 138.78, 142.22,
170.04; HRMS (FAB, m/z)

calcd for C
28
H
19
Br
2
N
2
O
2
S
2
636.9255, measured 636.9255.
Synthesis of the Poly(N-9-heptadecanyl-2,7-carbazole-
alt-3,6-bis(5-(4-(diphenylamino)phenyl)-2-thienyl)-1,4-
diphenylpyrrolo[3,2-b]pyrrole-2,5-dione) (P1): Carefully
purified 3,6-bis{5-[4-(diphenylamino)phenyl]-2-thienyl}-1,4-
diphenylpyrrolo[3,2-b]pyrrole-2,5-dione (8) (150 mg, 0.25
mmol), 2,7-bis(4',4',5',5'-tetramethyl-1',3',2'-dioxaborolan-2'-yl)-
N-9''-heptadecanylcarbazole (10) (160 mg, 0.25 mmol), and
(PPh
3
)
4
Pd(0) (3 mol %) were dissolved in a mixture of
toluene and aqueous 2 M K
2
CO
3
. The mixture was refluxed
with vigorous stirring for 3 days under argon atmosphere.
After 72 h, phenylboronic acid was added to the reaction
then 12 h later, bromobenzene was added and the reaction
mixture refluxed overnight to complete the end-capping
reaction. After cooling to room temperature, the mixture was
poured into methanol. The precipitated material was
recovered by filtration. The resulting solid material was
reprecipitated using 100 mL of THF/1.0 L of methanol
several times to remove residual amount of catalyst. The
resulting polymer was soluble in THF, CHCl
3
, ODCB and
toluene.
Synthesis of the Poly(N-9-heptadecanyl-2,7-carbazole-
alt-3,6-bis(5-(4-(diphenylamino)phenyl)-2-thienyl)-1,4-
bis(4-methylphenyl)pyrrolo[3,2-b]pyrrole-2,5-dione) (P2):
Carefully purified 3,6-bis{5-[4-(diphenylamino)phenyl]-2-
thienyl}-1,4-bis(4-methylphenyl)pyrrolo[3,2-b]pyrrole-2,5-
dione (9) (150 mg, 0.23 mmol), 2,7-bis(4',4',5',5'-tetramethyl-
1',3',2'-dioxaborolan-2'-yl)-N-9''-heptadecanylcarbazole (10)
(150 mg, 0.23 mmol), and (PPh
3
)
4
Pd(0) (3 mol %) were
dissolved in a mixture of toluene and aqueous 2 M K
2
CO
3
.
The mixture was refluxed with vigorous stirring for 3 days
under argon atmosphere. After 72 h, phenylboronic acid was
added to the reaction then 12 h later, bromobenzene was
added and the reaction mixture refluxed overnight to
complete the end-capping reaction. After cooling to room
temperature, the mixture was poured into methanol. The
precipitated material was recovered by filtration. The result-
ing solid material was reprecipitated using 100 mL of THF/
1.0 L of methanol several times to remove residual amount
of catalyst. The resulting polymer was soluble in THF,
CHCl
3
, ODCB and toluene.
Acknowledgments. This work was supported by the
National Research Foundation of Korea (NRF) grant funded
by the Korea government (MEST) (No. 2010-0015069) and
by Basic Science Research Program through the National
Research Foundation of Korea (NRF) funded by the
Ministry of Education, Science and Technology (No. 2011-
0010851).
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