Supporting Information Synthesis of All-Conjugated Diblock ...
Supporting Information
Synthesis of All-Conjugated Diblock Copolymers by Quasi-living Polymerization and Observation of Their Microphase Separation Yue Zhang1, Keisuke Tajima*1, Kouske Hirota1 and Kazuhito Hashimoto*1,2 1
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
2
HASHIMOTO Light Energy Conversion Project, ERATO, Japan Science and Technology Agency (JST)
[email protected]
S1
Experimental Synthesis All reagents were used as received, unless otherwise stated. 3-Bromothiophene, 1-bromohexane, 1bromo-2-ethylhexane, anhydrous THF, magnesium turnings, Ni(dppp)Cl2, iodine, N-bromosuccinimide (NBS), and i-PrMgCl in THF (2 mol/L) were purchased from Wako Pure Chemical Industries, Ltd. Iodobenzene diacetate was purchased from Kanto Chemical Co., Inc. 3-hexylthiophene, 2-bromo-3hexylthiophene, 2-bromo-3-hexyl-4-iodothiophene and poly(3-hexylthiophene) were synthesized as previously reported (ref. 4 in the main text).
3-(2-Ethylhexyl)thiophene (1) To a mixture of magnesium turnings (10.2 g, 0.42 mol), anhydrous THF (40 mL) and a small amount of iodine in a 300 mL flask, a solution of 2-ethylhexylbromide (79 g, 0.41 mol) in anhydrous THF (100 mL) was added slowly at 0 °C under N2. After refluxing for 1 h, the solution was added dropwise to a mixture of 3-bromothiophene (50 g, 0.31 mol), Ni(dppp)Cl2 (1.7 g, 3 mmol) and anhydrous THF (100 mL) placed in a 500 mL flask at 0 °C. After the mixture was stirred overnight at room temperature, the reaction was quenched by pouring cold HCl aq. (2 N) into the mixture. The product was extracted with CHCl3 and dried over anhydrous Mg2SO4. The crude product was further purified by column chromatography using hexane as the eluent to give a clear liquid (54 g, 90%). 1: 1H NMR (CDCl3, 500 MHz):
7.21-7.22 (m, 1H), 6.89-6.90 (m, 2H), 2.56 (d, J = 6.7 Hz, 2H),
1.55-1.56 (m, 1H), 1.19-1.32 (m, 8H), 0.82-0.91 (m, 6H).
2-Bromo-3-(2-ethylhexyl)thiophene (2) To 150 mL of THF solution of 1 (11.78 g, 60 mmol), N-bromosuccinimide (10.68 g, 60 mmol) was added portionwise at 0 °C and the mixture was stirred at 0 °C overnight. The organic fraction was extracted with water and CHCl3, washed with NaHCO3 aq., and dried over anhydrous Mg2SO4. Further purification by Kugelrohr distillation gave a transparent oil (16.32 g, 99%).
S2
2: 1H NMR (CDCl3, 500 MHz):
7.17-7.18 (d, 1H), 6.75-6.77 (d, 1H), 2.49-2.52 (d, 2H), 1.54-1.61
(1H), 1.23-1.32 (8H), 0.82-0.91 (6H).
2-Bromo-3-(2-ethylhexyl)-5-iodothiophene (3) To a solution of 2 (8.11 g, 29.5 mmol) in CH2Cl2 (150 mL), iodine (3.56 g, 14.1 mmol) and iodobenzene diacetate (4.51 g, 14.0 mmol) were successively added at 0 °C. The mixture was stirred at room temperature for 5 h. After 10% Na2S2O3 aq. was added, the mixture was extracted with Et2O. The organic layer was collected and dried over anhydrous MgSO4. After filtration, the organic solvents and iodobenzene were removed by evaporation under reduced pressure. The residue was purified by silica gel column chromatography using hexane as the eluent and further purified by vacuum distillation to give a pale-yellow oil (11.21 g, 95%). 3: 1H NMR (CDCl3, 500 MHz):
6.93 (s, 1H), 2.42-2.48 (2H), 1.54-1.56 (1H), 1.20-1.31(8H), 0.83-
0.91 (6H)
Poly(3-(2-ethylhexyl)thiophene) (4) A round-bottomed flask (100 mL) equipped with a three-way stopcock was dried by heating under reduced pressure and cooled to room temperature. 3 (1.60 g, 4 mmol) was placed in the flask under N2, and then evacuated under reduced pressure to remove water and oxygen inside. After the addition of dry THF (40 mL) into the flask via a syringe, the solution was mixed at 0 °C. 2 mol/L solution of i-PrMgCl in THF (2 mL, 4 mmol) was added via a syringe, and the mixture was stirred at 0 °C for 30 min. After the mixture was heated up to 35 °C, Ni(dppp)Cl2 catalyst (21.69 g, 0.04 mmol) was added in one portion. After the mixture was stirred for 8 h, the reaction was quenched by pouring of HCl aq. (50 wt%) into the mixture. After the polymer was extracted with CHCl3 and dried over anhydrous MgSO4, the solvent was removed by evaporation under reduced pressure. The crude polymer was successively washed by Soxhlet extraction using methanol and hexane, and finally extracted using CHCl3. The solvent was removed by evaporation to give a purple solid (0.55 g, 70%).
S3
4: 1H NMR (CDCl3, 500 MHz):
6.94 (s, 1H), 2.78-2.84 (2H), 1.66-1.74 (1H), 1.28-1.48 (8H), 0.88-
0.94 (t, 6H).
Poly(3-hexylthiophene-block-3-(2-ethylhexyl)thiophene) The feed molar ratio of 3-hexylthiophene and 3-(2-ethylhexyl)thiophene was changed from 50:50 to 75:25. The molecular weights were controlled by fixing the ratio of the amount of Ni catalyst to the total monomer amount at 1:100. The typical synthesis procedure of P(3HT-b-3EHT) diblock copolymers (feed molar ratio of 50:50) was as follows: two round-bottomed flasks (100 mL) equipped with a threeway stopcock were dried by heating under reduced pressure and cooled to room temperature. 2-Bromo3-hexyl-5-iodothiophene (0.75 g, 2 mmol) was placed in one of the flasks under N2, and then evacuated under reduced pressure to remove water and oxygen inside. After adding dry THF (20 mL) into the flask via a syringe, the solution was mixed at 0 °C. 2 mol/L solution of i-PrMgCl in THF (1 mL, 2 mmol) was added via a syringe, and the mixture was stirred at 0 °C for 30 min (solution A). In the other flask, 2 mmol of 3 was reacted with i-PrMgCl in the same manner (solution B). Solution A was heated up to 35 °C and Ni(dppp)Cl2 catalyst (21.69 g, 0.04 mmol) was added in one portion. After stirring for 1 h, solution B was added to solution A via a syringe, and the resulting solution was stirred for 7 h. The reaction was quenched by pouring HCl aq. (50wt%) into the solution.
The crude polymer was
successively washed by Soxhlet extraction using methanol and hexane, and finally extracted using CHCl3. The solvent was removed by evaporation to give a purple solid (0.52 g, 71%). P(3HT-b-3EHT) with a feed molar ratio of 75:25 was also synthesized in the same manner to give a purple solid (0.47 g, 67%) as the final product. The peaks observed at of thiophene rings, and the triplet peak at
6.98 and 6.94 ppm could be assigned to the sp2 CH
2.80 ppm and the doublet peak at
2.74 ppm to the sp3 CH2
attached to the thiophene rings in the regioregular P3HT and P3EHT blocks, respectively. From the integration of the peaks in both regions, the molar ratios of the P3HT and P3EHT segments were 56:44 and 83:17, which were close to the feed molar ratios of 50:50 and 75:25, respectively.
S4
Poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) The feed molar ratio of 3-hexylthiophene and 3-(2-ethylhexyl)thiophene was changed from 50:50 to 75:25. The molecular weights were controlled by fixing the ratio of the amount of Ni catalyst to the total monomer amount at 1:100. The typical synthesis procedure of P(3HT-co-3EHT) random copolymers (feed molar ratio of 50:50) was as follows: two round-bottomed flasks (100 mL) equipped with a threeway stopcock were dried by heating under reduced pressure and cooled to room temperature. 2-Bromo3-hexyl-5-iodothiophene (0.38 g, 1 mmol) and 3 (4.0g, 1 mmol) were placed in one of the flasks under N2, and then evacuated under reduced pressure to remove water and oxygen inside. After adding dry THF (10 mL) into the flask via a syringe, the solution was mixed at 0 °C. 2 mol/L solution of i-PrMgCl in THF (4 mL, 2 mmol) was added via a syringe, and the mixture was stirred at 0 °C for 30 min. Then, Reaction solution was heated up to 35 °C and Ni(dppp)Cl2 catalyst (10.84 g, 0.02 mmol) was added in one portion. After stirring for 2 h, the reaction was quenched by pouring HCl aq. (50wt%) into the solution. The crude polymer was successively washed by Soxhlet extraction using methanol and hexane, and finally extracted using CHCl3. The solvent was removed by evaporation to give a purple solid (0.18 g, 50%). P(3HT-co-3EHT) with a feed molar ratio of 75:25 was also synthesized in the same manner to give a purple solid (0.37 g, 82%) as the final product. The peaks observed at
6.98 and 6.94 ppm could
be assigned to the sp2 CH of thiophene rings, and the triplet peak at 2.80 ppm and the doublet peak at 2.74 ppm to the sp3 CH2 attached to the thiophene rings in the regioregular P3HT and P3EHT fractions, respectively. From the integration of the peaks in both regions, the molar ratios of the P3HT and P3EHT fractions were 56:44 and 75:25, which were close to the feed molar ratios of 50:50 and 75:25, respectively. We also measured GPC of the products after soxhlet extraction to obtain Mn of 30000 with PDIs of 1.2 for both the polymers.
Measurement Gel permeation chromatography (GPC) was performed using a Shimadzu Prominence system equipped with a UV detector using chloroform as the eluent at 40 °C. The chloroform solution was
S5
filtered using a PTFE filter (pore size: 1.0 µm) before sample injection. 1H NMR spectra in CDCl3 were measured using a JEOL Alpha FT-NMR spectrometer equipped with an Oxford superconducting magnet system (500 MHz). UV-vis spectra were recorded using a JACSO V-650 spectrometer. Differential scanning calorimetry (DSC) was performed using Rigaku DSC 8230 at a heating rate of 10 K min-1 under N2 flow. Tapping-mode atomic force microscopy (AFM) was performed with Nanoscope III (Digital Instruments, Inc.).
Complete Ref. 6b. Li, B.; Sauvé, G.; Iovu, M. C.; Jeffries-EL, M.; Zhang, R.; Cooper, J.; Santhanam, S.; Schultz, L.; Revelli, J. C.; Kusne, A. G.; Kowalewski, T.; Snyder, J. L.; Weiss, L. E.; Fedder, G. K.; McCullough, R. D.; Lambeth, D. N. Nano. Lett. 2006, 6, 1598.
S6
Br Mg, I2 Br
THF
S
NBS
Ni(dppp)Cl2, THF
THF
Br
S
S
I2, PhI(OAc)2 CH2Cl2
I
Br
S
Br
Br
Mg, I2 THF
S Ni(dppp)Cl2, THF
NBS THF
S
S
I2, PhI(OAc)2 CH2Cl2
I
S
Br
Br
Figure S1. Synthetic routes of the monomers for modified GRIM polymerization.
S7
i-PrMgCl I
S
Br
I
S
Br
Ni(dppp)Cl2
THF
Br
S
S
H n
Figure S2. Synthetic route of poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene)) (P3HT-co3EHT) random copolymers by modified GRIM polymerization
S8
(a)
(b)
(c)
(d)
(e)
((f)
7 Figure S3.
6 1
5
4 Chemical Shift / ppm
3
2
1
H NMR spectra of (a) poly(3-hexylthiophene) (P3HT), (b) poly(3-(2-
ethylhexyl)thiophene) (P3EHT), poly(3-hexylthiophene-block-3-(2-ethylhexyl)thiophene)) (P3HTb-3EHT) with block ratios of (c) 56:44 and (d) 83:17 and poly(3-hexylthiophene-co-3-(2ethylhexyl)thiophene)) (P3HT-co-3EHT) with molar ratios of (e) 56:44 and (f) 75:25 (500 MHz in chloroform-d at room temperature ) S9
25
30 35 Time / min
40
Figure S4. GPC chart of P(3HT-b-3EHT) with a block ratio of 83:17. The broken and solid lines show the GPC traces of the P3HT living polymer and P(3HT-b-3EHT), respectively.
S10
(a)
1
Heat Flow / mW
P3HT homopolymer
0
-1 50
100 150 o 200 Temperature / C
250
(b)
Heat Flow / mW
2
P3EHT homopolymer
1 0 -1 -2 50
100 150 o Temperature / C
200
250
Figure S5. Differential scanning calorimetry (DSC) measurement of (a) poly(3-hexylthiophene) (P3HT) and (b) poly(3-(2-ethylhexyl)thiophene) (P3EHT) homopolymer (scan rate: 10 K min-1).
S11
1.5
P(3HT-b-3EHT) diblock copolymer Heat Flow / mW
1.0 0.5 0.0 -0.5 -1.0 -1.5 50
100 150 200 o Temperature / C
250
Figure S6. Differential scanning calorimetry (DSC) measurements of poly(3-hexylthiophene-b-3(2-ethylhexyl)thiophene)) (P3HT-b-3EHT) with a block ratio of 83:17 (scan rate: 10 K min-1).
S12
(a)
Heat Flow / mW
4 2 0 -2
50
100 150 o Temperature / C
200
250
50
100 150 o Temperature / C
200
250
(b)
Heat Flow / mW
4
2
0
-2
-4
Figure S7. Differential scanning calorimetry (DSC) measurements of poly(3-hexylthiophene-co3-(2-ethylhexyl)thiophene)) (P3HT-co-3EHT)s with the unit ratios of (a) 56:44 and (b) 75:25 (scan rate: 10 K min-1).
S13
(a)
(b)
250 nm (c)
250 nm (d)
250 nm
250 nm
Figure S8. Atomic force microscopy (AFM) height (a and c) and phase (b and d) images of the thin films of the P(3HT-b-3EHT) copolymers with the block ratios of (a and b) 56:44 and (c and d) 83:17 after annealing at 240 °C (image size: 1 µm × 1 µm).
S14
(a)
(b)
250 nm (c)
250 nm (d)
250 nm 250 nm
250 nm
Figure S9. Atomic force microscopy (AFM) (a and c) height and (b and d) phase images of the thin films of the P(3HT-co-3EHT) with the unit ratios of (a and b) 56:44 and (c and d) 75:25 after annealing at 200 °C (image size: 1 µm × 1 µm).
S15
Synthesis of All-Conjugated Diblock Copolymers by Quasi-living Polymerization and Observation of Their Microphase Separation Yue Zhang1, Keisuke Tajima*1, Kouske Hirota1 and Kazuhito Hashimoto*1,2 1
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
2
HASHIMOTO Light Energy Conversion Project, ERATO, Japan Science and Technology Agency (JST)
[email protected]
S1
Experimental Synthesis All reagents were used as received, unless otherwise stated. 3-Bromothiophene, 1-bromohexane, 1bromo-2-ethylhexane, anhydrous THF, magnesium turnings, Ni(dppp)Cl2, iodine, N-bromosuccinimide (NBS), and i-PrMgCl in THF (2 mol/L) were purchased from Wako Pure Chemical Industries, Ltd. Iodobenzene diacetate was purchased from Kanto Chemical Co., Inc. 3-hexylthiophene, 2-bromo-3hexylthiophene, 2-bromo-3-hexyl-4-iodothiophene and poly(3-hexylthiophene) were synthesized as previously reported (ref. 4 in the main text).
3-(2-Ethylhexyl)thiophene (1) To a mixture of magnesium turnings (10.2 g, 0.42 mol), anhydrous THF (40 mL) and a small amount of iodine in a 300 mL flask, a solution of 2-ethylhexylbromide (79 g, 0.41 mol) in anhydrous THF (100 mL) was added slowly at 0 °C under N2. After refluxing for 1 h, the solution was added dropwise to a mixture of 3-bromothiophene (50 g, 0.31 mol), Ni(dppp)Cl2 (1.7 g, 3 mmol) and anhydrous THF (100 mL) placed in a 500 mL flask at 0 °C. After the mixture was stirred overnight at room temperature, the reaction was quenched by pouring cold HCl aq. (2 N) into the mixture. The product was extracted with CHCl3 and dried over anhydrous Mg2SO4. The crude product was further purified by column chromatography using hexane as the eluent to give a clear liquid (54 g, 90%). 1: 1H NMR (CDCl3, 500 MHz):
7.21-7.22 (m, 1H), 6.89-6.90 (m, 2H), 2.56 (d, J = 6.7 Hz, 2H),
1.55-1.56 (m, 1H), 1.19-1.32 (m, 8H), 0.82-0.91 (m, 6H).
2-Bromo-3-(2-ethylhexyl)thiophene (2) To 150 mL of THF solution of 1 (11.78 g, 60 mmol), N-bromosuccinimide (10.68 g, 60 mmol) was added portionwise at 0 °C and the mixture was stirred at 0 °C overnight. The organic fraction was extracted with water and CHCl3, washed with NaHCO3 aq., and dried over anhydrous Mg2SO4. Further purification by Kugelrohr distillation gave a transparent oil (16.32 g, 99%).
S2
2: 1H NMR (CDCl3, 500 MHz):
7.17-7.18 (d, 1H), 6.75-6.77 (d, 1H), 2.49-2.52 (d, 2H), 1.54-1.61
(1H), 1.23-1.32 (8H), 0.82-0.91 (6H).
2-Bromo-3-(2-ethylhexyl)-5-iodothiophene (3) To a solution of 2 (8.11 g, 29.5 mmol) in CH2Cl2 (150 mL), iodine (3.56 g, 14.1 mmol) and iodobenzene diacetate (4.51 g, 14.0 mmol) were successively added at 0 °C. The mixture was stirred at room temperature for 5 h. After 10% Na2S2O3 aq. was added, the mixture was extracted with Et2O. The organic layer was collected and dried over anhydrous MgSO4. After filtration, the organic solvents and iodobenzene were removed by evaporation under reduced pressure. The residue was purified by silica gel column chromatography using hexane as the eluent and further purified by vacuum distillation to give a pale-yellow oil (11.21 g, 95%). 3: 1H NMR (CDCl3, 500 MHz):
6.93 (s, 1H), 2.42-2.48 (2H), 1.54-1.56 (1H), 1.20-1.31(8H), 0.83-
0.91 (6H)
Poly(3-(2-ethylhexyl)thiophene) (4) A round-bottomed flask (100 mL) equipped with a three-way stopcock was dried by heating under reduced pressure and cooled to room temperature. 3 (1.60 g, 4 mmol) was placed in the flask under N2, and then evacuated under reduced pressure to remove water and oxygen inside. After the addition of dry THF (40 mL) into the flask via a syringe, the solution was mixed at 0 °C. 2 mol/L solution of i-PrMgCl in THF (2 mL, 4 mmol) was added via a syringe, and the mixture was stirred at 0 °C for 30 min. After the mixture was heated up to 35 °C, Ni(dppp)Cl2 catalyst (21.69 g, 0.04 mmol) was added in one portion. After the mixture was stirred for 8 h, the reaction was quenched by pouring of HCl aq. (50 wt%) into the mixture. After the polymer was extracted with CHCl3 and dried over anhydrous MgSO4, the solvent was removed by evaporation under reduced pressure. The crude polymer was successively washed by Soxhlet extraction using methanol and hexane, and finally extracted using CHCl3. The solvent was removed by evaporation to give a purple solid (0.55 g, 70%).
S3
4: 1H NMR (CDCl3, 500 MHz):
6.94 (s, 1H), 2.78-2.84 (2H), 1.66-1.74 (1H), 1.28-1.48 (8H), 0.88-
0.94 (t, 6H).
Poly(3-hexylthiophene-block-3-(2-ethylhexyl)thiophene) The feed molar ratio of 3-hexylthiophene and 3-(2-ethylhexyl)thiophene was changed from 50:50 to 75:25. The molecular weights were controlled by fixing the ratio of the amount of Ni catalyst to the total monomer amount at 1:100. The typical synthesis procedure of P(3HT-b-3EHT) diblock copolymers (feed molar ratio of 50:50) was as follows: two round-bottomed flasks (100 mL) equipped with a threeway stopcock were dried by heating under reduced pressure and cooled to room temperature. 2-Bromo3-hexyl-5-iodothiophene (0.75 g, 2 mmol) was placed in one of the flasks under N2, and then evacuated under reduced pressure to remove water and oxygen inside. After adding dry THF (20 mL) into the flask via a syringe, the solution was mixed at 0 °C. 2 mol/L solution of i-PrMgCl in THF (1 mL, 2 mmol) was added via a syringe, and the mixture was stirred at 0 °C for 30 min (solution A). In the other flask, 2 mmol of 3 was reacted with i-PrMgCl in the same manner (solution B). Solution A was heated up to 35 °C and Ni(dppp)Cl2 catalyst (21.69 g, 0.04 mmol) was added in one portion. After stirring for 1 h, solution B was added to solution A via a syringe, and the resulting solution was stirred for 7 h. The reaction was quenched by pouring HCl aq. (50wt%) into the solution.
The crude polymer was
successively washed by Soxhlet extraction using methanol and hexane, and finally extracted using CHCl3. The solvent was removed by evaporation to give a purple solid (0.52 g, 71%). P(3HT-b-3EHT) with a feed molar ratio of 75:25 was also synthesized in the same manner to give a purple solid (0.47 g, 67%) as the final product. The peaks observed at of thiophene rings, and the triplet peak at
6.98 and 6.94 ppm could be assigned to the sp2 CH
2.80 ppm and the doublet peak at
2.74 ppm to the sp3 CH2
attached to the thiophene rings in the regioregular P3HT and P3EHT blocks, respectively. From the integration of the peaks in both regions, the molar ratios of the P3HT and P3EHT segments were 56:44 and 83:17, which were close to the feed molar ratios of 50:50 and 75:25, respectively.
S4
Poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) The feed molar ratio of 3-hexylthiophene and 3-(2-ethylhexyl)thiophene was changed from 50:50 to 75:25. The molecular weights were controlled by fixing the ratio of the amount of Ni catalyst to the total monomer amount at 1:100. The typical synthesis procedure of P(3HT-co-3EHT) random copolymers (feed molar ratio of 50:50) was as follows: two round-bottomed flasks (100 mL) equipped with a threeway stopcock were dried by heating under reduced pressure and cooled to room temperature. 2-Bromo3-hexyl-5-iodothiophene (0.38 g, 1 mmol) and 3 (4.0g, 1 mmol) were placed in one of the flasks under N2, and then evacuated under reduced pressure to remove water and oxygen inside. After adding dry THF (10 mL) into the flask via a syringe, the solution was mixed at 0 °C. 2 mol/L solution of i-PrMgCl in THF (4 mL, 2 mmol) was added via a syringe, and the mixture was stirred at 0 °C for 30 min. Then, Reaction solution was heated up to 35 °C and Ni(dppp)Cl2 catalyst (10.84 g, 0.02 mmol) was added in one portion. After stirring for 2 h, the reaction was quenched by pouring HCl aq. (50wt%) into the solution. The crude polymer was successively washed by Soxhlet extraction using methanol and hexane, and finally extracted using CHCl3. The solvent was removed by evaporation to give a purple solid (0.18 g, 50%). P(3HT-co-3EHT) with a feed molar ratio of 75:25 was also synthesized in the same manner to give a purple solid (0.37 g, 82%) as the final product. The peaks observed at
6.98 and 6.94 ppm could
be assigned to the sp2 CH of thiophene rings, and the triplet peak at 2.80 ppm and the doublet peak at 2.74 ppm to the sp3 CH2 attached to the thiophene rings in the regioregular P3HT and P3EHT fractions, respectively. From the integration of the peaks in both regions, the molar ratios of the P3HT and P3EHT fractions were 56:44 and 75:25, which were close to the feed molar ratios of 50:50 and 75:25, respectively. We also measured GPC of the products after soxhlet extraction to obtain Mn of 30000 with PDIs of 1.2 for both the polymers.
Measurement Gel permeation chromatography (GPC) was performed using a Shimadzu Prominence system equipped with a UV detector using chloroform as the eluent at 40 °C. The chloroform solution was
S5
filtered using a PTFE filter (pore size: 1.0 µm) before sample injection. 1H NMR spectra in CDCl3 were measured using a JEOL Alpha FT-NMR spectrometer equipped with an Oxford superconducting magnet system (500 MHz). UV-vis spectra were recorded using a JACSO V-650 spectrometer. Differential scanning calorimetry (DSC) was performed using Rigaku DSC 8230 at a heating rate of 10 K min-1 under N2 flow. Tapping-mode atomic force microscopy (AFM) was performed with Nanoscope III (Digital Instruments, Inc.).
Complete Ref. 6b. Li, B.; Sauvé, G.; Iovu, M. C.; Jeffries-EL, M.; Zhang, R.; Cooper, J.; Santhanam, S.; Schultz, L.; Revelli, J. C.; Kusne, A. G.; Kowalewski, T.; Snyder, J. L.; Weiss, L. E.; Fedder, G. K.; McCullough, R. D.; Lambeth, D. N. Nano. Lett. 2006, 6, 1598.
S6
Br Mg, I2 Br
THF
S
NBS
Ni(dppp)Cl2, THF
THF
Br
S
S
I2, PhI(OAc)2 CH2Cl2
I
Br
S
Br
Br
Mg, I2 THF
S Ni(dppp)Cl2, THF
NBS THF
S
S
I2, PhI(OAc)2 CH2Cl2
I
S
Br
Br
Figure S1. Synthetic routes of the monomers for modified GRIM polymerization.
S7
i-PrMgCl I
S
Br
I
S
Br
Ni(dppp)Cl2
THF
Br
S
S
H n
Figure S2. Synthetic route of poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene)) (P3HT-co3EHT) random copolymers by modified GRIM polymerization
S8
(a)
(b)
(c)
(d)
(e)
((f)
7 Figure S3.
6 1
5
4 Chemical Shift / ppm
3
2
1
H NMR spectra of (a) poly(3-hexylthiophene) (P3HT), (b) poly(3-(2-
ethylhexyl)thiophene) (P3EHT), poly(3-hexylthiophene-block-3-(2-ethylhexyl)thiophene)) (P3HTb-3EHT) with block ratios of (c) 56:44 and (d) 83:17 and poly(3-hexylthiophene-co-3-(2ethylhexyl)thiophene)) (P3HT-co-3EHT) with molar ratios of (e) 56:44 and (f) 75:25 (500 MHz in chloroform-d at room temperature ) S9
25
30 35 Time / min
40
Figure S4. GPC chart of P(3HT-b-3EHT) with a block ratio of 83:17. The broken and solid lines show the GPC traces of the P3HT living polymer and P(3HT-b-3EHT), respectively.
S10
(a)
1
Heat Flow / mW
P3HT homopolymer
0
-1 50
100 150 o 200 Temperature / C
250
(b)
Heat Flow / mW
2
P3EHT homopolymer
1 0 -1 -2 50
100 150 o Temperature / C
200
250
Figure S5. Differential scanning calorimetry (DSC) measurement of (a) poly(3-hexylthiophene) (P3HT) and (b) poly(3-(2-ethylhexyl)thiophene) (P3EHT) homopolymer (scan rate: 10 K min-1).
S11
1.5
P(3HT-b-3EHT) diblock copolymer Heat Flow / mW
1.0 0.5 0.0 -0.5 -1.0 -1.5 50
100 150 200 o Temperature / C
250
Figure S6. Differential scanning calorimetry (DSC) measurements of poly(3-hexylthiophene-b-3(2-ethylhexyl)thiophene)) (P3HT-b-3EHT) with a block ratio of 83:17 (scan rate: 10 K min-1).
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(a)
Heat Flow / mW
4 2 0 -2
50
100 150 o Temperature / C
200
250
50
100 150 o Temperature / C
200
250
(b)
Heat Flow / mW
4
2
0
-2
-4
Figure S7. Differential scanning calorimetry (DSC) measurements of poly(3-hexylthiophene-co3-(2-ethylhexyl)thiophene)) (P3HT-co-3EHT)s with the unit ratios of (a) 56:44 and (b) 75:25 (scan rate: 10 K min-1).
S13
(a)
(b)
250 nm (c)
250 nm (d)
250 nm
250 nm
Figure S8. Atomic force microscopy (AFM) height (a and c) and phase (b and d) images of the thin films of the P(3HT-b-3EHT) copolymers with the block ratios of (a and b) 56:44 and (c and d) 83:17 after annealing at 240 °C (image size: 1 µm × 1 µm).
S14
(a)
(b)
250 nm (c)
250 nm (d)
250 nm 250 nm
250 nm
Figure S9. Atomic force microscopy (AFM) (a and c) height and (b and d) phase images of the thin films of the P(3HT-co-3EHT) with the unit ratios of (a and b) 56:44 and (c and d) 75:25 after annealing at 200 °C (image size: 1 µm × 1 µm).
S15
