Supporting Information Available for
Synthesis and Optical Properties of Poly(p-benzamide)s bearing Oligothiophene on Amide
Nitrogen Atom through Alkylene Spacer
Koji Takagi,* Katsuya Nobuke, Yuma Nishikawa, and Ryohei Yamakado
Department of Materials Science and Engineering, Graduate School of Engineering,
Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan
*Corresponding
author
Phone: +81-52-735-5264, E-Mail: takagi.koji@nitech.ac.jp
Contents
1. Monomer syntheses
S2
2. UV and PL spectra
S14
3. Reference
S16
S1
1. Monomer syntheses
Scheme S1. Synthetic route to M1
Synthesis of 5-hexyl-2,2’-bithiophene-5’-carboxyaldehyde
g
h
f
0.0001
1.7246
1.6913
1.6729
1.6537
1.5569
1.4186
1.4147
1.4103
1.3755
1.3312
1.2681
1.2601
0.9262
0.8945
0.8626
2.8508
2.8138
2.7757
6.7502
6.7320
7.6497
7.6301
7.2598
7.1910
7.1724
7.1525
9.8367
To a THF solution (14 mL) of 5-hexyl-2,2’-bithiophene1 (1.1 g, 5.2 mmol) was added dropwise n-BuLi
in hexane (3.1 mL, 5.1 mmol) at -78 °C, and the temperature was gradually increased to room
temperature. After 30 min, DMF (0.40 mL, 5.7 mmol) was added and the mixture was stirred for 3
hours. Iced-water was added and an aqueous phase was extracted with CH2Cl2. The combined organic
phase was dried over MgSO4 and solvents were removed by rotary evaporator. The crude product was
purified by SiO2 chromatography (hexane/ethyl acetate=2/1, Rf=0.7) to obtain pale yellow oil in 0.91 g
(63% yield).
c b
e
Ha
S
CH3(CH2)3CH2CH2
S
d c
O
g
PPM
8.0
6.0
4.0
h
2.0
3.241
6.493
2.125
f
2.067
e
1.041
c d
2.060
1.039
b
1.000
a
0.0
Figure S1. 1H-NMR spectrum of 5-hexyl-2,2’-bithiophene-5’-carboxyaldehyde in CDCl3.
9.84 (s, 1H), 7.64 (d, 1H, J=3.9 Hz), 7.17 (2H), 6.74 (d, 1H, J=3.7 Hz), 2.81 (t, 2H, J=7.6 Hz), 1.69 (m,
2H), 1.48~1.23 (6H), 0.90 (t, 3H, J=6.6 Hz).
Synthesis of ethyl 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoate
A toluene solution (20 mL) of ethyl 4-aminobenzoate (1.1 g, 6.8 mmol), 5-hexyl-2,2’-bithiophene-5’carboxyaldehyde (1.3 g, 4.5 mmol), and p-TsOH•H2O (0.51 g, 2.7 mmol) was heated to reflux in DeanStark apparatus to carry out the dehydration condensation for 6 hours. After cooling to room temperature,
NaBH(OAc)3 (1.4 g, 6.8 mmol) was added and the mixture was stirred overnight. Saturated aq. Na2CO3
was added and an aqueous phase was extracted with ethyl acetate. The combined organic phase was
dried over MgSO4 and solvents were removed by rotary evaporator. The crude product was purified by
recrystallization from hexane/ethyl acetate to obtain pale yellow solid in 1.4 g (71% yield). Mp: 114116 °C.
S2
1.7101
1.6963
1.6941
1.6874
1.6796
1.6673
1.6636
1.6614
1.6437
1.6269
1.6292
1.6046
1.5894
1.5477
1.4328
1.4251
1.4057
1.3923
1.3721
1.3569
1.3206
1.2564
0.9147
0.9101
0.9069
0.9012
0.8868
0.8530
0.0001
2.8075
2.7699
2.7319
4.5091
4.3674
4.3322
4.2967
4.2610
4.2550
7.9116
7.9050
7.8684
7.2589
7.2526
6.9424
6.9249
6.9080
6.8871
6.8705
6.6583
6.6154
g
f
i
h
CH2CH2(CH2)3CH3
b
S
b
S
d c a
c a
8.0
e
f
7.0
6.0
5.0
4.0
3.0
h i
g
1.996
2.107
3.033
d e
2.947
3.037
b c
2.040
PPM
h
O
2.0
3.206
d
a
O
HN
9.916
c
2.695
b
1.0
0.0
Figure S2. 1H-NMR spectrum of ethyl 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoate in CDCl3.
7.88 (d, 2H, J=7.7 Hz), 6.90 (3H), 6.63 (3H), 4.51 (3H), 4.31 (q, 2H, J=7.6 Hz), 2.77 (t, 2H, J=7.3 Hz),
1.66 (m, 2H), 1.45~1.20 (6H)+(t, 3H, J=6.9 Hz), 0.89 (t, 3H, J=6.5 Hz).
Synthesis of 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoic acid
e
g
f
1.3906
1.3814
1.3739
1.3616
1.3513
1.3163
1.2614
1.2587
0.9157
0.9084
0.9061
0.9018
0.8860
0.8547
0.8322
0.0000
1.6949
1.6857
1.6642
1.6471
1.6417
1.6289
1.6274
1.6249
2.8091
2.7725
2.7347
4.5345
7.2585
6.9498
6.9321
6.9145
6.8982
6.8808
6.6773
6.6632
6.6431
6.6343
7.9666
7.9232
Ethyl 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoate (0.70 g, 1.6 mmol) and 2 M aq. NaOH (7 mL)
in methanol (13 mL) and THF (13 mL) was heated to 50 °C for 6 hours. After cooling to room
temperature, 1 M aq. HCl was added to acidify the system and extracted with ethyl acetate. The organic
phase was dried over MgSO4 and solvents were removed by rotary evaporator. The obtained pale yellow
solid (0.62 g, 95% yield) was used for the next reaction without further purification. Mp: 147-150 °C.
h
CH2CH2(CH2)3CH3
b
S
b
S
d c
OH
7.0
6.0
5.0
4.0
3.0
g h
f
2.0
3.078
e
2.064
3.027
d
6.193
a
b c
3.024
1.999
PPM
O
HN
c
a
a
2.147
c
2.070
b
1.0
0.0
Figure S3. 1H-NMR spectrum of 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoic acid in CDCl3.
S3
7.94 (d, 2H, J=9.0 Hz), 6.91 (3H), 6.65 (3H), 4.53 (s, 2H), 2.77 (t, 2H, J=7.1 Hz), 1.66 (m, 2H),
1.46~1.16 (6H), 0.88 (t, 3H, J=6.4 Hz).
Synthesis of phenyl 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoate (M1)
i
g h
1.7566
1.7509
1.7441
1.7368
1.7319
1.7172
1.7040
1.7060
1.6981
1.6933
1.6856
1.6690
1.6474
1.6427
1.6327
1.6116
1.6004
1.5945
1.5963
1.4563
1.4500
1.4392
1.4419
1.4067
1.3989
1.3864
1.3633
1.3275
1.3216
1.2787
1.2751
0.9567
0.9203
0.9122
0.9080
0.8885
0.8674
0.8571
0.0002
2.8142
2.7767
2.7395
4.6332
4.6297
4.6217
4.6087
4.6029
4.5943
4.5892
4.5544
4.5572
8.0603
8.0164
7.4458
7.4424
7.4334
7.4059
7.3667
7.2554
7.2309
7.2080
7.2014
7.1653
6.9547
6.9366
6.9182
6.9052
6.8874
6.7142
6.6699
6.6531
6.6486
To a DMF solution (1.8 mL) of 4-((5”-hexyl-2,2’-bithienyl)methyl)aminobenzoic acid (0.26 g, 0.61
mmol) was added a DMF solution (1.8 mL) of phenol (70 mg, 0.75 mmol), DMAP (96 mg, 0.78 mmol),
and p-TsOH•H2O (118 mg, 0.62 mmol) at 0 °C. After stirring for 10 min, a DMF solution (3.0 mL) of
EDC•HCl (160 mg, 0.81 mmol) was added and the mixture was heated to 50 °C overnight. Water was
added and an aqueous phase was extracted with CH2Cl2. The combined organic phase was washed with
1 M aq. HCl and saturated aq. NaHCO3, then dried over MgSO4. Solvents were removed by rotary
evaporator to give crude product which was purified by SiO2 chromatography (CH2Cl2/ethyl acetate=9/1,
Rf=0.7) to obtain pale yellow solid in 0.21 g (71% yield). Mp: 168-170 °C. Anal. Calcd. for
C29H31NO2S2: C, 71.13 %; H, 6.38 %; N, 2.86 %; S, 13.10 %. Found : C, 70.58 %; H, 6.36 %; N,
2.64 %; S, 13.50 %.
j
CH2CH2(CH2)3CH3
d
d
S
S
d
e
f e a
O
HN
f
e a
c b
c
O
7.0
6.0
5.0
h
4.0
3.0
2.0
j
3.311
i
6.529
2.605
1.995
g
3.113
3.062
2.154
PPM
f
d e
3.128
bc
3.535
a
2.002
c b
1.0
0.0
Figure S4. 1H-NMR spectrum of M1 in CDCl3.
8.04 (d, 2H, J=8.4 Hz), 7.40 (t, 2H, J=7.9 Hz), 7.20 (3H), 6.67 (3H), 4.55 (3H), 2.78 (t, 2H, J=7.3 Hz),
1.67 (m, 2H), 1.50~1.21 (6H), 0.89 (t, 3H, J=6.3 Hz).
S4
160.0
120.0
80.0
14.1138
22.5991
31.5826
30.1803
28.7683
42.9207
77.6918
77.0566
76.4208
112.0401
132.3047
129.3764
126.1157
125.5044
124.7550
123.4056
122.6450
121.9418
118.3025
139.8339
145.5956
151.6806
PPM
40.0
Figure S5. 13C-NMR spectrum of M1 in CDCl3.
% Transmittance
165.2, 151.3, 150.1, 138.4, 137.9, 137.0, 133.2, 132.5, 129.4, 127.9, 127.3, 125.5, 124.7, 124.2, 124.0,
121.9, 118.5, 116.7, 110.9, 43.5, 31.8, 29.3, 29.2, 29.0, 27.1, 22.7, 14.1.
3600
3100
2600
2100
Wavenumber (cm-1)
1600
1100
600
Figure S6. IR spectrum of M1 (ATR).
3354, 2926, 2853, 1695, 1594, 1525, 1285, 1169.
S5
Scheme S2. Synthetic route to M2
Synthesis of 5-hexyl-5’-(3-bromopropyl)-2,2’-bithiophene
f
PPM
7.0
6.0
5.0
4.0
de
f
3.0
0.0000
1.7014
1.6683
1.6302
1.5354
1.4069
1.4044
1.3954
1.3826
1.3667
1.3205
1.2602
1.2571
0.9199
0.8888
0.8558
2.0
g h
i
3.154
1.979
c
2.003
1.904
a b
Br
c
6.232
a
d
1.993
S
b
2.2659
2.2324
2.1981
2.1641
b
S
CH3(CH2)3CH2CH2
3.0013
2.9658
2.9303
2.8093
2.7725
2.7342
3.4808
3.4487
3.4165
a
e
1.927
g
2.000
h
1.941
i
5.2970
7.2568
6.9105
6.8929
6.7147
6.6973
6.6576
6.6401
To a mixture of n-BuLi in hexane (5.0 mL, 8.0 mmol) and TMEDA (1.2 mL, 8.0 mmol) was added
dropwise a THF solution (130 mL) of 5-hexyl-2,2’-bithiophene (2.0 g, 8.0 mmol) at 0 °C, and the
temperature was gradually increased to room temperature. After 30 min, 1,3-dibromopropane (3.3 mL,
32 mmol) was added and the mixture was stirred overnight. Iced-water was added and an aqueous phase
was extracted with diethyl ether. The combined organic phase was dried over MgSO4 and solvents were
removed by rotary evaporator. The crude product was purified by SiO2 chromatography (hexane,
Rf=0.3) to obtain yellow oil in 0.80 g (27% yield).
1.0
0.0
Figure S7. 1H-NMR spectrum of 5-hexyl-5’-(3-bromopropyl)-2,2’-bithiophene in CDCl3.
6.90 (d, 2H, J=3.3 Hz), 6.71 (d, 1H, J=3.4 Hz), 6.65 (d, 1H, J=3.7 Hz), 3.44 (t, 2H, J=6.4 Hz), 2.97 (t,
2H, J=7.1 Hz), 2.77 (t, 2H, J=7.3 Hz), 2.20 (m, 2H), 1.67 (m, 2H), 1.46~1.20 (6H), 0.89 (t, 3H, J=6.20
Hz).
Synthesis of ethyl 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoate
A HMPA solution (3 mL) of 5-hexyl-5’-(3-bromopropyl)-2,2’-bithiophene (0.75 g, 2.0 mmol) and ethyl
4-aminobenzoate (0.67 g, 4.0 mmol) was heated to 125 °C overnight. Iced-water was added and the
mixture was stirred at 0 °C for 3 hours. The precipitate was collected which was washed with 50% aq.
EtOH to obtain yellow solid in 0.88 g (96% yield). Mp: 108-110 °C.
S6
-0.0043
1.5448
1.3884
1.3749
1.3530
1.3177
0.9162
0.8853
2.0043
m
2.9045
2.7721
2.7343
l
3.2674
3.2376
k
4.3246
4.2890
7.2552
6.9086
6.8916
6.6852
6.6595
6.6410
6.5509
6.5069
7.8795
7.8364
i
CH2CH2(CH2)3CH3
c
b
S
S
h
O
l
HN
PPM
7.0
6.0
5.0
g hi
4.0
3.0
j
k
l
2.0
m
2.951
1.018
2.139
2.001
1.933
e f
e
9.218
d a
b cd
1.972
2.051
a
O
1.963
f
2.351
g d a
j
2.113
c
1.995
2.064
b
1.0
0.0
Figure S8. 1H-NMR spectrum of ethyl 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoate in CDCl3.
7.86 (d, 2H, J=8.9 Hz), 6.90 (d, 2H, J=3.7 Hz), 6.66 (2H), 6.53 (d, 2H, J=9.3 Hz), 4.30 (q, 2H, J=7.4
Hz), 4.09 (s, 1H), 3.25 (t, 2H, J=6.3 Hz), 2.91 (t, 2H, J=6.7 Hz) 2.77 (t, 2H, J=7.4 Hz), 2.01 (m, 2H),
1.66 (m, 2H), 1.42~1.23 (6H)+(t, 3H, J=7.4 Hz), 0.89 (t, 3H, J=6.3 Hz).
Synthesis of 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoic acid
1.6776
1.6742
1.6711
1.6583
1.6352
h
i
2.241
1.3876
1.3826
1.3668
1.3598
1.3246
1.2809
1.2709
1.2684
1.2623
1.2589
0.9197
0.8897
0.8655
0.8581
0.0000
2.0530
2.0192
1.9845
1.9790
k
2.225
ｊ
i
g
3.3090
3.2740
3.2395
2.9518
2.9495
2.9146
2.8775
2.8121
2.7765
2.7374
7.2589
6.9154
6.8979
6.6938
6.6760
6.6715
6.6644
6.6466
6.5711
6.5276
7.9358
7.8925
Ethyl 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoate (0.83 g, 1.8 mmol) and 2 M aq. NaOH (8 mL)
in methanol (14 mL) and THF (14 mL) was heated to 50 °C for 6 hours. After cooling to room
temperature, 1 M aq. HCl was added to acidify the system and extracted with ethyl acetate. The organic
phase was dried over MgSO4 and solvents were removed by rotary evaporator. The obtained yellow
solid (0.76 g, 97% yield) was used for the next reaction without further purification. Mp: 135-138 °C.
CH2CH2(CH2)3CH3
c
S
b
S
b
f
c
h
e d a
O
HN
PPM
7.0
6.0
5.0
4.0
3.0
2.0
3.091
j k
6.883
fg
1.993
e
1.957
1.935
b cd
1.983
2.005
a
OH
1.960
2.148
d a
1.0
0.0
Figure S9. 1H-NMR spectrum of 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoic acid in CDCl3.
S7
7.91 (d, 2H, J=8.5 Hz), 6.91 (d, 2H, J=3.5 Hz), 6.67 (2H), 6.54 (d, 2H, J=8.8 Hz), 3.27 (t, 2H, J=6.7 Hz),
2.91 (t, 2H, J=7.2 Hz) 2.78 (t, 2H, J=7.4 Hz), 2.02 (m, 2H), 1.67 (m, 2H), 1.46~1.21 (6H), 0.89 (t, 3H,
J=6.2 Hz).
Synthesis of phenyl 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoate (M2)
1.7086
1.7059
1.6944
1.6969
1.6863
1.6880
1.6783
1.6735
1.6756
1.6677
1.6645
1.6603
1.6565
1.6534
1.6454
1.6489
1.6389
1.6308
1.6262
1.6201
1.5322
1.4043
1.3944
1.3970
1.3901
1.3825
1.3792
1.3737
1.3713
1.3659
1.3571
1.3214
1.3167
1.2950
1.2717
1.2658
1.2626
1.2582
hi
j
k
2.208
0.9278
0.9227
0.9150
0.9091
0.9038
0.9002
0.8879
0.8821
0.8628
0.8590
0.8549
0.8528
0.8468
2.0729
2.0705
2.0671
2.0620
2.0415
2.0307
2.0332
2.0235
2.0012
1.9974
1.9938
m
2.025
l
2.9608
2.9547
2.9498
2.9269
2.9208
2.9243
2.9154
2.9077
2.8967
2.8909
2.8868
2.8838
2.8203
2.8111
2.8056
2.7800
2.7752
2.7692
2.7499
2.7430
2.7374
2.7314
k
3.3277
3.3257
3.3195
3.3217
3.2972
3.2931
3.2776
3.2677
3.2569
3.2539
i
4.2175
4.2115
4.2140
4.2062
4.1978
4.2007
6.7006
6.6955
6.6913
6.6862
6.6794
6.6759
6.6711
6.6639
6.6554
6.6529
6.6480
6.6341
6.6124
6.6050
6.5831
6.5693
6.5639
6.9213
6.9082
6.9057
8.0326
8.0290
8.0256
8.0207
7.9923
7.9899
7.9862
7.4009
7.3628
7.2762
7.2574
7.2286
7.2209
7.2170
7.2019
7.1836
7.1716
7.1628
7.1568
To a DMF solution (6 mL) of 4-((5”-hexyl-2,2’-bithienyl)propyl)aminobenzoic acid (0.76 g, 1.8 mmol)
was added a DMF solution (6 mL) of phenol (0.19 g, 2.1 mmol), DMAP (0.26 g, 2.1 mmol), and pTsOH•H2O (0.32 g, 1.7 mmol) at 0 °C. After stirring for 10 min, a DMF solution (9 mL) of EDC•HCl
(0.43 g, 2.2 mmol) was added and the mixture was heated to 50 °C overnight. Water was added and an
aqueous phase was extracted with CH2Cl2. The combined organic phase was washed with 1 M aq. HCl
and saturated aq. NaHCO3, then dried over MgSO4. Solvents were removed by rotary evaporator to give
crude product which was purified by SiO2 chromatography (CH2Cl2/ethyl acetate=9/1, Rf=0.7) to obtain
pale yellow solid in 0.88 g (60% yield). Mp: 133-135 °C. Anal. Calcd. for C28H29NO2S2: C, 71.53 %; H,
6.60 %; N, 2.78 %; S, 12.73 %. Found : C, 71.44 %; H, 6.57 %; N, 2.69 %; S, 13.03 %.
CH2CH2(CH2)3CH3
e
S
d
S
d
h
7.0
e
O
a
1.087
6.0
5.0
c
c b
g
f
3.990
2.066
PPM
1.953
b c d e
2.585
a
1.965
f
c b
4.0
3.0
2.0
l m
2.961
O
HN
5.955
a
1.996
1.997
ge
j
2.045
e
1.0
0.0
Figure S10. 1H-NMR spectrum of M2 in CDCl3.
8.01 (d, 2H, J=8.3 Hz), 7.40 (t, 2H, J=7.6 Hz), 7.20 (3H), 6.91 (2H), 6.73~6.52 (4H), 4.21 (s, 1H), 3.29
(t, 2H, J=6.3 Hz), 2.93 (t, 2H, J=6.9 Hz), 2.78 (t, 2H, J=7.6 Hz), 2.03 (m, 2H), 1.67 (m, 2H), 1.46~1.22
(m, 6H), 0.89 (t, 3H, -CH3, J=6.9 Hz).
S8
160.0
120.0
80.0
14.1443
31.6172
30.8883
30.1962
28.8055
27.5683
22.6294
42.4578
77.7291
77.0933
76.4592
76.3228
111.5638
145.0978
142.6117
136.0604
134.9627
132.3383
129.3795
125.4690
125.2895
124.6978
122.9290
122.7344
121.9908
117.3062
152.4643
151.3671
165.3958
PPM
40.0
Figure S11. 13C-NMR spectrum of M2 in CDCl3.
% Transmittance
165.4, 152.5, 151.4, 145.1, 142.6, 136.1, 135.0, 132.3, 129.4, 125.5, 125.3, 124.7, 122.9, 122.7, 122.0,
117.3, 111.6, 42.5, 31.6, 30.9, 30.2, 28.8, 27.6, 22.6, 14.1.
3600
3100
2600
2100
Wavenumber (cm-1)
1600
1100
600
Figure S12. IR spectrum of M2 (ATR).
3354, 2925, 1684, 1595, 1524, 1284, 1168, 1079, 794.
S9
Scheme S3. Synthetic route to M3
Synthesis of 5-hexyl-5”-(3-bromopropyl)-2,2’:5’,2”-terthiophene
S
S
a
7.0
1.793
6.0
5.0
4.0
d
a
c
2.232
4.941
ab
PPM
0.0001
1.7151
1.7116
1.7058
1.7031
1.6993
1.6931
1.6794
1.6715
1.6559
1.6523
1.6413
1.6248
1.5320
1.4171
1.4111
1.4071
1.3996
1.3933
1.3955
1.3904
1.3753
1.3719
1.3679
1.3649
1.3276
1.2636
0.9239
0.9207
0.9125
0.8933
0.8603
2.2433
2.2096
2.1752
f
S
de
3.0
Br
c
f
g h
2.0
i
3.171
CH3(CH2)3CH2CH2
b
6.692
a
2.145
a
e
1.998
g
1.732
h
1.822
b
i
3.0186
2.9841
2.9486
2.8230
2.8257
2.7866
2.7485
3.5609
3.5565
3.5286
3.5247
3.4886
3.4565
3.4244
5.1519
5.1479
5.1406
6.7434
6.7395
6.7259
6.7140
6.7024
6.6815
6.6683
6.6642
7.2561
7.2355
7.2287
7.2176
7.2101
7.2036
7.1860
7.1649
7.1466
7.0783
7.0631
7.0435
7.0363
7.0249
7.0093
6.9980
6.9717
To a mixture of n-BuLi in hexane (5.0 mL, 8.1 mmol) and TMEDA (1.2 mL, 8.0 mmol) was added
dropwise a THF solution (130 mL) of 5-hexyl-2,2’:5’,2”-terthiophene1 (2.6 g, 7.9 mmol) at 0 °C, and
the temperature was gradually increased to room temperature. After 30 min, 1,3-dibromopropane (3.3
mL, 32 mmol) was added and the mixture was stirred overnight. Iced-water was added and an aqueous
phase was extracted with diethyl ether. The combined organic phase was dried over MgSO4 and solvents
were removed by rotary evaporator. The crude product was purified by SiO2 chromatography (hexane,
Rf=0.2 and then CH2Cl2, Rf=0.8) to obtain yellow oil in 1.7 g (47% yield). Although the purity was not
high, the product was used for the next reaction.
1.0
0.0
Figure S13. 1H-NMR spectrum of 5-hexyl-5”-(3-bromopropyl)-2,2’:5’,2”-terthiophene in CDCl3.
6.97 (4H), 6.73 (d, 1H, J=3.2 Hz), 6.67 (d, 1H, J=3.6 Hz), 3.46 (t, 2H, J=6.6 Hz), 2.97 (t, 2H, J=7.5 Hz),
2.79 (t, 2H, J=7.5 Hz), 2.22 (m, 2H), 1.68 (m, 2H), 1.48~1.19 (6H), 0.89 (t, 3H, J=7.7 Hz).
Synthesis of ethyl 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoate
A HMPA solution (2.6 mL) of 5-hexyl-5”-(3-bromopropyl)-2,2’:5’,2”-terthiophene (0.80 g, 1.8 mmol)
and ethyl 4-aminobenzoate (0.59 g, 3.5 mmol) was heated to 125 °C overnight. Iced-water was added
and the mixture was stirred at 0 °C for 3 hours. The precipitate was collected which was washed with
50% aq. EtOH. The crude product was purified by SiO2 chromatography (CH2Cl2, Rf=0.4) to obtain
yellow solid in 0.45 g (47% yield). Mp: 108-110 °C.
S10
c
b
b
b
S
S
h
O
l
HN
7.0
6.0
5.0
4.0
3.0
k
l m
2.0
2.895
j
9.594
g hi
2.154
e f
2.366
e
0.984
2.307
2.489
b cd
5.106
2.446
O
d a
2.210
f
2.320
g d a
j
2.391
1.986
c
PPM
1.7139
1.7026
1.7069
1.6995
1.6963
1.6861
1.6736
1.6716
1.6667
1.6597
1.6514
1.6539
1.6421
1.6450
1.6364
1.6340
1.6303
1.5486
1.3892
1.3843
1.3539
1.3224
1.2770
1.2692
1.2647
1.2601
1.2529
0.9178
0.9126
0.9088
0.8934
0.8894
0.8671
0.8584
0.0001
S
b
a
2.0518
2.0482
2.0324
2.0139
1.9818
1.9798
m
2.9588
2.9532
2.9556
2.9509
2.9202
2.8879
2.8836
2.8264
2.8212
2.8149
2.8177
2.7868
2.7809
2.7443
2.7484
l
3.2970
3.2945
3.2808
3.2758
3.2612
3.2564
3.2546
3.2280
k
4.3666
4.3625
4.3529
4.3274
4.2910
4.2605
4.2554
4.1097
4.1064
4.1002
4.0977
4.0905
4.0925
4.0874
4.0854
4.0793
4.0728
7.8817
7.8434
7.2551
7.0112
7.0058
7.0007
6.9725
6.7055
6.7014
6.6999
6.6924
6.6870
6.6845
6.6731
6.6682
6.5540
6.5569
6.5145
i
CH2CH2(CH2)3CH3
1.0
0.0
Figure S14. 1H-NMR spectrum of ethyl 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoate in
CDCl3.
7.86 (d, 2H, J=8.5 Hz), 6.98 (4H), 6.69 (2H), 6.53 (d, 2H, J=8.9 Hz), 4.30 (q, 2H, J=7.4 Hz), 4.09 (s,
1H), 3.25 (m, 2H), 2.91 (t, 2H, J=6.7 Hz), 2.77 (t, 2H, J=7.4 Hz), 2.01 (m, 2H), 1.66 (m, 2H), 1.42~1.23
(6H)+(t, 3H, J=7.4 Hz), 0.89 (t, 3H, J=6.3 Hz).
Synthesis of 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoic acid
CH2CH2(CH2)3CH3
c
S
b
b
b
S
S
f
O
☆
HN
j
7.0
f g
1.998
1.941
2.052
e
6.0
5.0
4.0
3.0
h
i
2.0
k
3.083
cd
3.956
1.969
PPM
d a
6.293
b
OH
1.945
g ed a
2.159
c
1.965
2.002
b
a
1.3908
1.3881
1.3810
1.3732
1.3663
1.3283
1.3266
1.3077
1.2849
1.2670
1.2590
0.9235
0.8928
0.8593
0.8571
0.0704
0.0001
k
1.6796
1.6769
1.6407
j
2.0554
2.0459
2.0216
1.9865
1.9839
h i
3.8485
3.3004
3.2790
3.2660
3.2307
2.9584
2.9224
2.8883
2.8855
2.8232
2.7869
2.7485
7.2577
6.9737
6.9572
6.7147
6.6973
6.6838
6.6656
6.5762
6.5329
7.8832
7.8394
Ethyl 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoate (0.64 g, 1.2 mmol) and 2 M aq. NaOH (6
mL) in methanol (10 mL) and THF (10 mL) was heated to 50 °C for 6 hours. After cooling to room
temperature, 1 M aq. HCl was added to acidify the system and extracted with ethyl acetate. The organic
phase was dried over MgSO4 and solvents were removed by rotary evaporator. The obtained yellow
solid (0.62 g, 99% yield) was used for the next reaction without further purification.
1.0
0.0
Figure S15. 1H-NMR spectrum of 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoic acid in CDCl3.
S11
The signal marked with star indicates the contamination of methyl 4-((5-hexyl-2,2’:5’,2”terthienyl)propyl)aminobenzoate.
Synthesis of phenyl 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoate (M3)
d
S
d
d
S
0.961
1.947
1.988
6.0
5.0
4.0
1.6810
1.6777
1.6746
1.6420
1.5375
1.3939
1.3759
1.3710
1.3663
1.3304
0.9232
0.9153
0.9086
0.8934
0.8719
0.8672
0.8640
0.8580
0.0001
m
h
i j
3.0
k
l
2.0
n
2.562
c
c b
g
5.159
O
1.805
c b
2.096
f a
ef
4.054
2.062
3.123
1.997
O
HN
2.005
1.717
hf a
g
7.0
2.0768
2.0412
2.0062
i
j
2.078
d
PPM
2.9765
2.9397
2.9043
2.8240
2.8265
2.7885
2.7867
2.7500
S
e
b c
n
CH2CH2(CH2)3CH3
d
a
m
3.3379
3.3340
3.3239
3.3148
3.3087
3.3024
3.2974
3.2954
3.2802
3.2732
3.2623
k l
e
4.2277
4.2226
4.2155
8.0380
7.9947
7.4430
7.4062
7.3679
7.2561
7.2395
7.2287
7.2052
7.1687
7.0094
6.9801
6.7284
6.7111
6.6842
6.6743
6.6664
6.6158
6.5718
To a DMF solution (5 mL) of 4-((5-hexyl-2,2’:5’,2”-terthienyl)propyl)aminobenzoic acid (0.66 g, 1.2
mmol) was added a DMF solution (4 mL) of phenol (0.13 g, 1.4 mmol), DMAP (0.18 g, 1.5 mmol), and
p-TsOH•H2O (0.22 g, 1.2 mmol) at 0 °C. After stirring for 10 min, a DMF solution (6 mL) of EDC•HCl
(0.29 g, 1.5 mmol) was added and the mixture was heated to 50 °C overnight. Water was added and an
aqueous phase was extracted with CH2Cl2. The combined organic phase was washed with 1 M aq. HCl
and saturated aq. NaHCO3, then dried over MgSO4. Solvents were removed by rotary evaporator to give
crude product which was purified by SiO2 chromatography (CH2Cl2/ethyl acetate=9/1, Rf=0.7) and
recrystallization from CH2Cl2/ethyl acetate to obtain pale yellow solid in 0.34 g (58% yield). Mp: 145146 °C. Anal. Calcd. for C34H35NO2S3: C, 69.71 %; H, 6.02 %; N, 2.39 %; S, 16.42 %. Found : C,
69.23 %; H, 5.75 %; N, 2.32 %; S, 17.09 %.
1.0
0.0
Figure S16. 1H-NMR spectrum of M3 in CDCl3.
8.02 (d, 2H, J=8.7 Hz), 7.41 (t, 2H, J=7.2 Hz), 7.20 (3H), 6.98 (4H), 6.72 (d, 1H, J=3.7 Hz), 6.67 (d, 1H,
J=3.5 Hz), 6.59 (d, 2H, J=8.3 Hz), 4.22 (s, 1H), 3.30 (m, 2H), 2.94 (t, 2H, J=7.5 Hz), 2.79 (t, 2H, J=6.5
Hz), 2.04 (m, 2H), 1.68 (m, 2H), 1.48~1.21 (6H), 0.89 (t, 3H, J=5.6 Hz).
S12
160.0
120.0
80.0
14.1452
31.6088
30.8896
30.2341
28.8074
27.6036
22.6232
42.4550
77.7250
77.2812
77.0911
76.4547
152.4360
151.3583
145.6098
143.3144
136.5163
135.7205
135.3595
134.5165
132.3410
129.3792
125.4708
124.8598
123.7935
123.3374
123.2946
121.9861
117.3539
111.5715
165.3799
PPM
40.0
Figure S17. 13C-NMR spectrum of M3 in CDCl3.
% Transmittance
165.4, 152.4, 151.4, 145.6, 143.3, 136.5, 135.7, 135.4, 134.5, 132.3, 129.4, 125.5, 124.9, 123.8, 123.5,
123.4, 123.3, 122.0, 117.4, 111.6, 42.5, 31.6, 30.9, 30.2, 28.8, 27.6, 22.6, 14.1.
3600
3100
2600
2100
Wavenumber (cm-1)
1600
1100
600
Figure S18. IR spectrum of M3 (ATR).
3371, 2926, 1685, 1595, 1521, 1194, 1167, 1078.
S13
Absoebance & Emission/a.u.
2. UV and PL spectra
250
300
350
400
450
500
550
600
Wavelength/nm
Absoebance & Emission/a.u.
Figure S19. UV and PL spectra of polyM1 in THF (solid line: 10-5 M and broken line: 10-4 M relative to
bithiophene) (Excitation wavelengths were those of absorption maxima).
250
300
350
400
450
Wavelength/nm
500
550
600
Figure S20. UV and PL spectra of p-calix[3]amide in THF (10-5 M relative to bithiophene) (Excitation
wavelengths were those of absorption maxima).
S14
b
240
Emission/a.u.
Absorbance/a.u.
a
280
320
360
400
Wavelength/nm
440
480
360
400
440
480
520
560
600
Wavelength/nm
Figure S21. (a) UV and (b) PL spectra of polyM3 (solid line) and reference sample Y (dotted line) in
THF (10-5 M relative to bithiophene) (Excitation wavelengths were those of absorption maxima).
S15
3. Reference
1. Kirchmeyer, S.; Ponomarenko, S. J. Mater. Chem. 2002, 13, 197–202.
S16