Supplementary Materials for
Synthesis and optical properties of conjugated polymers
bearing 1,8-difunctionalized carbazole unit
Koji TAKAGI,1,* Hidenobu TAKAO,1 and Tsuyoshi NAKAGAWA1
1
Department of Materials Science and Engineering, Graduate School of Engineering,
Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan
*
To whom correspondence should be addressed (Phone: +81-52-735-5264, Facsimile: +81-52-735-7254,
E-mail: takagi.koji@nitech.ac.jp)
Contents
1. Synthesis of imine-functionalized monomer 4 …………………………………..…………...
2
2. Synthesis of 1,3-oxazoline-functionalized monomer 6 ……………………………................
5
3. Synthesis of pyridine-functionalized 9-H monomer 8 and 9-Me monomer 9 ………………..
8
4. Synthesis of phenyl-functionalized monomer 11 …………………………………………….
10
5. UV-vis and PL spectra of conjugated polymer P0 …………………………………………...
15
6. References …………………………………………………………………………………….
16
1
1. Synthesis of imine-functionalized monomer 4
Scheme S1.
1,8-Dicyanocarbazole (1)1
To a 1-methyl-2-pyrrolidinone (NMP, 100 mL) solution of
1,8-dibromocarbazole (3.25 g, 10.0 mmol) was added CuCN (2.69 g, 30.0 mmol), and the mixture was
heated to reflux for 3 h.
was collected.
After cooling to room temperature, iced water was added and the precipitate
The obtained solid was washed with H2O/ethylenediamine (500 mL, 3/1 in volume
ratio) for 1 h and then dissolved in ethyl acetate.
MgSO4.
The solution was washed with brine and dried over
The evaporation of solvent gave pale yellow solid which was used without further
purification.
Yield: 2.06 g (95%).
1
H-NMR (, CDCl3) 7.43 (2H, t, J=7.7Hz), 7.97 (2H, d,
J=7.7Hz), 8.60 (2H, d, J=7.7Hz), 13.2 (1H, s).
1,8-Diformylcarbazole (2)2
To a toluene (23 mL) solution of 1 (0.652 g, 3.00 mmol) was added
dropwise a toluene solution of diisobutylaluminum hydride (DIBALH) (1.0 M, 6.30 mL, 6.30 mmol) at
-78 °C.
The mixture was stirred overnight while the temperature was gradually increased to room
temperature.
After toluene was evaporated, 1 M aq. H2SO4 was added and the mixture was heated to
reflux for 2 h.
The solution was neutralized with 1 M aq. NaOH and the aqueous phase was extracted
with ethyl acetate.
The organic phase was washed with brine and dried over MgSO 4.
2
The
evaporation of solvent gave pale yellow solid which was purified by SiO2 chromatography (CH2Cl2,
Rf=0.25) to obtain yellow solid.
Yield 0.302 g (46%).
Mp. 204-207 °C.
1
H-NMR (, CDCl3)
7.55 (2H, t, J=7.8Hz), 8.16 (2H, d, J=7.1Hz), 8.65 (2H, d, J=7.8Hz), 10.3 (2H, s), 11.6 (1H, s).
3,6-Dibromo-1,8-diformylcarbazole (3)
To a N,N-dimethylformamide (DMF, 15 mL) solution of 2
(0.235 g, 1.05 mmol) was added N-bromosuccinimide (NBS) (0.935 g, 5.25 mmol), and the mixture was
heated to reflux for 6 h under dark.
After DMF was evaporated, distilled water was added and the
aqueous phase was extracted with CH2Cl2.
NaHCO3 and brine, then dried over MgSO4.
The organic phase was washed with saturated aq.
The evaporation of solvent gave pale yellow solid which
was washed with methanol to obtain pale yellow solid.
1
Yield 0.185 g (46%).
Mp. 308-311 °C.
H-NMR (, CDCl3) 8.36 (2H, t, J=1.7Hz), 8.94 (2H, d, J=1.7Hz), 10.3 (2H, s), 11.6 (1H, s).
3,6-Dibromo-1,8-bis((mesitylimino)methyl)carbazole (4)3
To a CHCl3 (20 mL) solution of 3 (0.152 g,
0.400 mmol) were added a few grains of molecular sieves 4Å, mesitylamine (0.337 mL, 2.40 mmol),
and acetic acid (0.4 mL).
After the mixture was heated to reflux for 4 d, the solution was evaporated
to dryness to give yellow solid which was purified by SiO2 chromatography (CH2Cl2:hexane=1:2,
Rf=0.70) to obtain yellow solid.
Yield 0.188 g (76%).
Mp. 273-276 °C.
1
H-NMR (, CDCl3)
2.07 (12H, s), 2.27 (6H, s), 6.83 (4H, s), 7.73 (2H, s), 8.32 (2H, s), 8.41 (2H, s), 12.6 (1H, s).
C-NMR (, CDCl3) 18.3, 20.8, 112.0, 121.1, 124.1, 125.9, 127.5, 128.9, 132.4, 133.5, 137.0, 162.0.
13
IR (ATR) 636, 822, 853, 917, 980, 1062, 1142, 1195, 1305, 1376, 1469, 1599, 1633, 2912, 3372.
Found: C, 62.54; H, 4.81; N, 6.58 %. Calcd for C32H29Br2N3: C, 62.45; H, 4.75; N, 6.83 %.
3
0.0000
1.5361
2.2708
2.0731
7.2546
6.8293
7.7255
8.4125
8.3194
12.6156
12.6119
f)
e)
b) N
d)
Br
c)
6.0
5.0
Br
4.064
8.0
7.0
4.0
3.0
2.0
77.6634
77.0294
76.3977
112.0186
121.1041
9.0
128.8510
127.4694
125.8928
124.1404
10.0
133.4969
132.4317
136.9769
11.0
2.013
2.062
2.057
1.000
12.0
162.0055
PPM 13.0
f)
1.0
0.0
20.7729
18.2932
b) c) d)
a)
H
N
g)
N
6.193
12.48
e)
a)
g)
b)
c)
a) N
Ar-C(10C)
H
N
N
c)
Br
Br
a)
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
110
Transmittance(%)
PPM 160.0
b)
100
90
80
70
60
50
3600
3100
2600
2100
1600
-1
Wavenumbers(cm )
4
1100
600
20.0
2. Synthesis of 1,3-oxazoline-functionalized monomer 6
Scheme S2.
3,6-Dibromo-1,8-dicyanocarbazole (5)
To a DMF (20 mL) solution of 1 (0.652 g, 3.00 mmol) were
added NaHCO3 (0.630 g, 7.50 mmol) and Br2 (0.773 mL, 15.0 mmol), and the mixture was stirred at
room temperature for 22 h under dark.
After DMF was evaporated, distilled water was added and the
precipitate was collected by the filtration.
The solid was dissolved in ethyl acetate that was washed
with saturated aq. Na2S2O3, saturated aq. NaHCO3, and brine, then dried over MgSO4.
evaporation of solvent gave pale yellow solid which was used without further purification..
1.01 g (90%).
1
The
Yield
H-NMR (, CDCl3) 8.23 (2H, d, J=1.3Hz), 8.91 (2H, d, J=1.2Hz), 13.6 (1H, s).
3,6-Dibromo-1,8-bis(4’,4’-dimethyl-1’,3’-oxazolyl)carbazole (6)4
A flask containing ZnCl2 (0.102 g,
0.750 mmol) was heated under the reduced pressure at 110 °C for 10 h and purged with the nitrogen.
5 (94.0 mg, 0.250 mmol), chlorobenzene (5 mL), and 2-amino-2-methyl-1-propanol (0.072 mL, 0.750
mmol) were added and the mixture was heated to reflux for 48 h.
added and the mixture was stirred for 1 h.
An ethylenediamine solution was
An aqueous phase was extracted with CH2Cl2, and the
combined organic phase was washed with saturated aq. NaHCO3 and brine, then dried over MgSO4.
The evaporation of solvent gave pale yellow solid which was purified by the recrystallization from
CHCl3 to obtain pale yellow solid.
Yield 0.085 g (65%).
Mp. 323-326 °C.
1
H-NMR (, CDCl3)
1.49 (12H, s), 4.19 (4H, s), 7.99 (2H, d, J=1.7Hz), 8.22 (2H, d, J=1.4Hz), 12.3 (1H, s).
5
13
C-NMR (,
CDCl3) 28.8, 67.9, 78.7, 111.5, 112.3, 124.0, 126.0, 128.5, 138.0, 160.0.
IR (ATR) 623, 641, 684, 722,
751, 865, 940, 991, 1056, 1086, 1142, 1192, 1273, 1312, 1360, 1476, 1614, 1645, 2892, 2963, 3314.
-0.0000
1.4922
4.1914
7.2607
8.2304
8.2234
7.9950
7.9865
12.2469
Found: C, 50.96; H, 4.00; N, 7.82 %. Calcd for C22H21Br2N3O3: C, 50.89; H, 4.08; N, 8.09 %.
e)
d)
e)
a) N
O
H
N
N
O
c)
Br
d)
Br
b)
O
N
6.0
78.7365
77.5839
76.9488
76.3144
5.0
4.0
3.0
2.0
1.0
0.0
28.7627
7.0
67.9319
8.0
112.2632
111.5145
c)
9.0
128.5241
126.0246
123.9728
10.0
138.0035
11.0
160.0437
12.0
12.41
2.076
2.020
1.000
PPM
4.084
b) c)
a)
b)
N O
H
N
a)
Me
Br
Br
Ar-C(6C)
b)
c)
a)
PPM170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
6
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
Transmittance(%)
110
100
90
80
70
60
50
3600
3100
2600
2100
1600
Wavenumbers(cm-1)
7
1100
600
3. Synthesis of pyridine-functionalized 9-H monomer 8 and 9-Me monomer 9
Scheme S3.
1,8-Bis(pyridine-2-yl)carbazole (7)5
A toluene (6 mL) solution of 1,8-dibromocarbazole (0.390 g,
1.20 mmol), 2-(n-tributylstannyl)pyridine (1.33 g, 3.60 mmol), and Pd(PPh3)4 (0.14 g, 0.12 mmol)was
heated to reflux for 48 h.
CHCl3.
After distilled water was added, an aqueous phase was extracted with
The combined organic phase was washed with saturated aq. NaHCO3 and brine, then dried
over MgSO4.
The evaporation of solvent gave brown oil which was purified by SiO2 chromatography
(CH2Cl2:hexane=1:1, Rf=0.50) to obtain pale orange solid that was finally washed with hexane.
0.207 g (54%).
1
Yield
H-NMR (, CDCl3) 7.28-7.53 (4H), 8.01 (2H, t, J=7.2Hz), 8.21 (2H, d, J=7.2Hz),
8.25-8.48 (4H), 9.02 (2H, d, J=3.1Hz), 13.5 (1H, s).
3,6-Dibromo-1,8-bis(pyridine-2’-yl)carbazole (8)
To a THF (15 mL) solution of 7 (0.193 g, 0.600
mmol) was added NBS (0.214 g, 1.20 mmol) at 0°C, and the mixture was stirred for 40 h while the
temperature was gradually increased to room temperature.
aqueous phase was extracted with CH2Cl2.
dried over MgSO4.
methanol.
After saturated aq. NaHCO3 was added, an
The combined organic phase was washed with brine, then
The evaporation of solvent gave pale yellow solid which was finally washed with
Yield 0.274 g (96%).
Mp. 210-213 °C.
1
H-NMR (, CDCl3) 7.32 (2H, t, J=5.8Hz),
7.85 (2H, td, J=7.7Hz, 1.6Hz), 7.98 (2H, d, J=8.2Hz), 8.06 (2H, d, J=1.5Hz), 8.20 (2H, s), 8.89 (2H, d,
J=4.1Hz), 13.3 (1H, s).
137.3, 149.0, 156.1.
C-NMR (, CDCl3) 111.9, 120.3, 122.0, 122.5, 124.1, 124.8, 126.5, 136.8,
13
IR (ATR) 642, 785, 851, 1030, 1084, 1133, 1205, 1242, 1265, 1312, 1393, 1434,
8
1446, 1479, 1586, 3052, 3333.
Found: C, 54.31; H, 2.04; N, 8.39 %. Calcd for C22H13Br2N3: C,
g)
b)
f)
N a) N
H
N
e)
d)
d) e)
c)
Br
c)
10.4
10.0
9.6
9.2
8.8
2.003
2.122
2.018
2.000
8.4
g)
8.0
7.6
7.2
111.8618
10.8
120.2983
11.2
122.5206
121.9688
11.6
124.7941
124.0702
12.0
126.4837
12.4
137.3192
136.7633
12.8
148.9564
13.2
156.0599
PPM 13.6
f)
2.000
0.988
b)
2.046
Br
a)
7.3494
7.3236
7.3168
7.2880
7.2599
8.2000
8.0654
8.0580
8.0042
7.9637
7.8972
7.8891
7.8595
7.8522
7.8199
7.8116
8.9007
8.8801
13.3233
55.14; H, 2.73; N, 8.77 %.
b)
Ar-C(11C)
N
H
N
N
a)
b)
Br
Br
a)
PPM 156.0
152.0
148.0
144.0
140.0
136.0
132.0
128.0
9
124.0
120.0
116.0
112.0
108.0
104.0
Transmittance(%)
110
100
90
80
70
60
3600
3100
2600
2100
1600
Wavenumbers(cm-1)
3,6-Dibromo-1,8-bis(pyridine-2’-yl)-9-methylcarbazole (9)
1100
600
To a THF (3 mL) solution of 8 (0.144 g,
0.300 mmol) was added NaH (60% oil suspension, 0.013 g, 0.330 mmol), and the mixture was stirred
for 1 h.
CH3I (28.0 L, 0.450 mmol) was added under dark, and the mixture was stirred for overnight.
After THF was evaporated, distilled water was added and the solution was extracted with CHCl 3, which
was washed with brine, then dried over MgSO4.
The evaporation of solvent gave pale yellow solid
which was purified by SiO2 chromatography (CH2Cl2 then ethyl acetate).
Mp. 248-251 °C.
1
Yield 0.120 g (81%).
H-NMR (, CDCl3) 2.86 (3H, s), 7.30 (2H, t, J=6.0Hz), 7.59 (2H, d, J=7.8Hz),
7.64 (2H, d, J=2.1Hz), 7.80 (2H, td, J=7.8Hz, 1.8Hz), 8.22 (2H, d, J=1.9Hz), 8.73 (2H, d, J=4.5Hz).
C-NMR (, CDCl3) 38.3, 112.6, 122.4, 123.1, 124.7, 125.7, 127.1, 131.8, 136.4, 139.8, 149.4, 157.2.
13
IR (ATR) 641, 743, 785, 816, 858, 1035, 1122, 1189, 1256, 1299, 1371, 1397, 1428, 1476, 1586, 1726,
2953, 3055.
10
PPM 160.0
150.0
140.0
130.0
2.067
3.033
2.141
d)e)
Br
120.0
3600
6.4
110.0
3100
6.0
100.0
5.6
5.2
90.0
80.0
2600
11
38.3027
6.8
77.6808
77.0446
76.4102
7.2
112.5808
7.6
127.0915
125.7335
124.7110
123.1409
122.3738
8.0
2.010
2.069
b)
131.8402
8.4
136.4136
2.031
a)
139.8194
149.3982
157.1569
PPM
Transmittance(%)
2.000
a)
N Me N
N
b)
4.8
b)
70.0
2100
f)
g)
c)
e)
60.0
g)
d)
Br
c)
f)
4.4
4.0
a)
50.0
Wavenumbers(cm )
1600
-1
3.6
40.0
3.2
Br
30.0
1100
2.8
20.0
110
100
90
80
70
60
600
2.4
b)
N Me N
a)
N
Ar-C(11C)
Br
Me
10.0
2.8565
7.3301
7.3094
7.3049
7.2975
7.2926
7.2613
8.2255
8.2162
7.8462
7.8378
7.8078
7.7995
7.7696
7.7611
7.6490
7.6395
7.6107
7.5719
8.7419
8.7211
8.7188
4. Synthesis of phenyl-functionalized monomer 11
Scheme S4.
1,8-diphenylcarbazole (10)5
To a toluene/EtOH (24 mL/2.4 mL) solution of 1,8-dibromocarbazole
(0.195 g, 0.60 mmol) and phenylboronic acid (0.219 g, 1.80 mmol) were added Pd(PPh3)4 (35 mg, 30
mol) and 2 M aq. Na2CO3 (6 mL), and the system was heated to reflux for 24 h.
was added, an aqueous phase was extracted with CHCl3.
with brine, then dried over MgSO4.
After 1 M aq. HCl
The combined organic phase was washed
The evaporation of solvent followed by SiO2 chromatography
(CH2Cl2:hexane=1:2, Rf=0.60) gave colorless solid.
Yield 0.180 g (92%).
1
H-NMR (, CDCl3)
7.30-7.85 (14H), 8.12 (2H, t, J=7.5Hz), 8.54 (1H, s).
3,6-Dibromo-1,8-diphenylcarbazole (11)
To a THF (10 mL) solution of 10 (0.128 g, 0.40 mmol) was
added NBS (0.142 g, 0.80 mmol) at 0°C, and the mixture was stirred overnight while the temperature
was gradually increased to room temperature.
phase was extracted with CH2Cl2.
over MgSO4.
The combined organic phase was washed with brine, then dried
The evaporation of solvent followed by washing with methanol gave colorless solid.
Yield 0.187 g (98%).
J=0.6Hz), 8.47 (1H, s).
136.2, 137.3.
After saturated aq. NaHCO3 was added, an aqueous
Mp. 228-231 °C.
1
H-NMR (, CDCl3) 7.40-7.65 (12H, Ar), 8.16 (2H, d,
C-NMR (, CDCl3) 113.3, 122.3, 124.6, 126.9, 128.0, 128.3, 129.1, 129.5,
13
IR (ATR) 644, 705, 739, 767, 856, 1018, 1225, 1262, 1292, 1387, 1405, 1445, 1473,
1496, 1580, 3056, 3471.
Found: C, 60.12; H, 2.86; N, 2.94 %. Calcd for C24H15Br2N: C, 60.41; H,
12
PPM
164.0
160.0
156.0
8.4
Br
152.0
8.2
148.0
144.0
140.0
12.22
H
N
8.0
136.0
7.8
132.0
13
128.0
124.0
113.2753
8.6
122.3255
8.8
Br
124.6341
PPM
b)
129.5198
129.0794
128.2940
128.0283
126.8804
137.2864
136.1956
Br
2.000
1.028
7.6
120.0
116.0
7.2593
7.4885
7.4600
7.4388
7.4261
7.6295
7.5927
7.5778
7.5696
7.5263
8.1616
8.1586
8.4674
3.17; N, 2.94 %.
a)
Ar)
b)
a)
7.4
7.2
H
N
Ar-C(10C)
Br
112.0
108.0
104.0
Transmittance(%)
110
100
90
80
70
60
50
3600
3100
2600
2100
1600
Wavenumbers(cm-1)
14
1100
600
5. UV-vis and PL spectra of conjugated polymer P0
(left: UV-vis spectrum and right: PL spectrum)
15
6. References
1.
T. Suzuki, A. Kinoshita, H. Kawada, and M. Nakada Synlet, 2003, 4, 570-572.
2.
I. Hogan, P. D. Jenkins, and M. Sainsbury Tetrahedron, 1990, 46, 2943-2964.
3.
G. J. P. Britovsek, V. C. Gibson, O. D. Hoarau, S. K. Spitzmesser, A. J. P. White, and D. J.
Williams Inorg. Chem., 2003, 42, 3454-3465.
4.
M. Inoue, T. Suzuki, and M. Nakada J. Am. Chem. Soc., 2003, 125, 1140-1141.
5.
M. S. Mudadu, A. N. Singh, and R. P. Thummel J. Org. Chem., 2008, 73, 6513-6520.
6.
M. J. Sienkowska, H. Monobe, P. Kaszynski, and Y. Shimizu J. Mater. Chem., 2007, 17,
1392-1398.
16