Supporting Information for：

Donor−Acceptor Copolymers Containing Phthalazinone–

Thiophene Structure Synthesized by Low-cost Copper-

catalyzed Ullmann Polymerization Jianhua Han,1 Haoyue Yin,1

Cheng Liu,1 Jinyan Wang,2* Xigao Jian2

1. Polymer Science & Materials, Chemical Engineering College, Dalian University of Technoloy, Dalian, 116024, China.

2. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China.

E-mail: wangjinyan@dlut.edu.cn

Table of Contents

1. The detailed experimental synthesis procedures for the monomers

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

2. 1H/13C -NMR(calculated Mn)/ and GPC spectrum of monomers and polymers

3. HPLC-MS spectrum of polymerized products

4. DSC and CV curves of polymers

1. The detailed experimental synthesis procedures for the monomers

S

Br

S

C12H25

S

C12H25

Br Br

a1 a2

HN H

N

BrBr

N

BrBr

C12H25

SBr

SMgBr

SS

S SSS

Br

Br

b1 b2

c1 c2

Br

3,6-dibromo-9H-carbazole(a1). NBS( 4.1 mmol) was added to a mixture of 9H-

carbazole ( 2.0 mmol) and silica gel in 10 ml of CH2Cl2 while cooling on ice. The

reactionmixture was stirring for 12 h and subsequently poured into 200 ml of ice

water. The product was extracted with CH2Cl2 and the combined organic layers were

washed with water. The organic extacts were dried over anhydrous MgSO4,

evaporated and purified with column chromatography on silica gel with hexane as the

eluent to give 3,6-dibromo-9H-carbazole (yield: 95%, HPLC>99.0 %).1H-NMR (400

MHz, DMSO) δ 11.61 (s, 1H), 8.44 (d, J = 1.1 Hz, 1H), 7.54 (dd, J = 8.8, 1.5 Hz, 1H),

7.48 (d, J = 8.7 Hz, 1H).

3,6-dibromo-9-dodecyl-9H-carbazole(a2): To a solution of 3,6-dibromo-9H-

carbazole ( 2.0 mmol) of mixture of DMSO (5 ml) and H2O (2 ml) was added

K2CO3(3.0 mmol), TBAB(0.3 mmol) and bromododecane ( 2.1 mmol). The reaction

mixture was stirring at 100 oC for 1 h. After cooling to room temperature, the product

was extracted and washed with dichloromethane, sodium carbonate solution, and

water. The organic extacts were dried over anhydrous MgSO4, evaporated and

purified with column chromatography on silica gel with hexane as the eluent to give

3,6-dibromo-9-dodecyl-9H-carbazole (yield 96%, HPLC>99.0%).1H-NMR (400 MHz,

CDCl3) δ 8.00 (d, J = 1.7 Hz, 2H), 7.46 (dd, J = 8.7, 1.9 Hz, 2H), 7.13 (d, J = 8.7 Hz,

2H), 4.07 (t, J = 7.1 Hz, 2H), 1.85 – 1.55 (m, 2H), 1.52 – 1.02 (m, 18H), 1.00 – 0.84

(m, 3H). 13C-NMR (101 MHz, CDCl3) δ 139.22 (s), 128.95 (s), 123.37 (s), 123.16 (s),

111.92 (s), 110.32 (s), 43.27 (s), 31.99 (s), 29.77 – 29.29 (m), 28.87 (s), 27.25 (s),

22.78 (s), 14.22 (s).

2,2':5',2''-terthiophene(b1): thiophen-2-ylmagnesium bromide (2M in diethyl ether)

(2.0 mmol) was added to a mixture of 2,4-dibromothiopene (1.0 mmol) and

Ni(dppp)Cl2 (0.1 mmol) in 10 ml of dry ether while cooling on ice. The reaction

mixture was refluxed for 12 h and subsequently poured into 200 ml of ice water

containing 2 mL of concentrated HCl. The product was extracted with ether and the

combined organic layers were washed with water and brine, successively. The organic

extacts were dried over anhydrous MgSO4, evaporated and purified with

recrystallization from n-hexane to give 2,2':5',2''-terthiophene (yield 60%,

HPLC>99.0 %). 1H-NMR (400 MHz, CDCl3) δ 7.22 (dd, J = 5.1, 1.1 Hz, 1H), 7.17

(dd, J = 3.6, 1.1 Hz, 1H), 7.08 (s, 1H), 7.02 (dt, J = 6.7, 3.3 Hz, 1H).

5,5''-dibromo-2,2':5',2''-terthiophene(b2): To a solution of 2,2':5',2''-terthiophene (2.0

mmol) of mixture of chloroform (15 ml) and acetic acid (7 ml) was added N-

bromosuccinimide (4.2 mmol). The reaction mixture was stirring at RT for 12 h. After

cooling to room temperature, the product was extracted and washed with

dichloromethane, sodium carbonate solution, and water. The organic extacts were

dried over anhydrous MgSO4, evaporated and purified with recrystallization from n-

hexane: methanol(1:1) to give 5,5''-dibromo-2,2':5',2''-terthiophene.(yield 60%,

HPLC>98.0 %). 1H-NMR (400 MHz, CDCl3) δ 6.99 (s, 1H), 6.97 (d, J = 3.9 Hz, 1H),

6.91 (d, J = 3.9 Hz, 1H).

3-dodecylthiophene(c1): Dodecylmagnesiumbromide (2M in diethyl ether) (2.1 mmol)

was added to a mixture of 3-bromothiopene (2 mmol) and Ni(dppp)Cl2 (0.1 mmol) in

10 ml of dry ether while cooling on ice. The reaction mixture was refluxed for 12 h

and subsequently poured into 200 ml of ice water containing 2 mL of concentrated

HCl. The product was extracted with ether and the combined organic layers were

washed with water and brine, successively. The organic extacts were dried over

anhydrous MgSO4, evaporated and purified with column chromatography on silica gel

with hexane as the eluent to give 3-dodecylthiophene (yield 96%,HPLC>99.0%). 1H-

NMR (400 MHz, CDCl3) δ 7.22 (dd, J = 4.9, 2.9 Hz, 1H), 7.00 – 6.85 (m, 2H), 2.71 –

2.56 (m, 2H), 1.62 (dd, J = 14.8, 7.1 Hz, 2H), 1.30 (d, J = 16.8 Hz, 18H), 0.91 (d, J =

6.7 Hz, 3H).

2,5-dibromo-3-dodecylthiophene(c2). To a solution of 3-dodecylthiophene (2.0 mmol)

of mixture of chloroform (5 ml) and acetic acid (2 ml) was added N-

bromosuccinimide (4.2 mmol). The reaction mixture was stirring at RT for 12 h. After

cooling to room temperature, the product was extracted and washed with

dichloromethane, sodium carbonate solution, and water. The organic extacts were

dried over anhydrous MgSO4, evaporated and purified with column chromatography

on silica gel with hexane as the eluent to give 2,5-dibromo-3-dodecylthiophene (yield

96%). 1H-NMR (400 MHz, CDCl3) δ 6.97 (s, 1H), 2.79 – 2.58 (m, 2H), 1.76 (dd, J =

14.0, 6.8 Hz, 2H), 1.52 (d, J = 9.3 Hz, 18H), 1.12 (d, J = 7.1 Hz, 3H). 13C-NMR (101

MHz, CDCl3) δ 142.90 (s), 130.89 (s), 110.49 (s), 108.09 (s), 32.13 (s), 30.05 – 29.44

(m), 29.33 (s), 22.91 (s), 14.32 (s).

2. 1H/13C -NMR(calculated Mn)/ and GPC spectrum of monomers and polymers

-1012345678910111213ppm

140814-2HJH-KZBrin DMSO 1H

1.00

0.96

0.92

0.50

A (d)7.48

B (dd)7.54

C (d)8.44

D (s)11.61

7.47

7.49

7.53

7.53

7.55

7.56

8.44

8.44

11.61

Figure S1. The 1H-NMR of a1

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0ppm

140912-45KZZL12in CDCl3 1H

1.59

9.31

1.02

0.99

1.02

1.01

1.00

A (m)0.86

B (m)1.23

C (m)1.71

D (t)4.07

E (d)7.13

F (dd)7.46

G (d)8.00

0.85

0.86

0.87

0.87

0.88

1.19

1.23

1.28

1.70

1.71

1.73

4.05

4.07

4.08

7.12

7.14

7.20

7.45

7.45

7.47

7.47

8.00

8.00

-100102030405060708090100110120130140150160170180190200210ppm

140912-45KZZL12in CDCl3 13C

14.22

22.78

27.25

28.87

29.39

29.41

29.53

29.61

29.67

31.99

43.27

76.80

77.12

77.43

110.32

111.92

123.16

123.37

128.95

139.22

Figure S2. The 1H-NMR and 13C-NMR of a2

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0ppm

130730-24han jian hua 1in CDCl3 1H

1.00

1.01

1.00

0.99

A (dt)7.02

B (s)7.08

C (dd)7.17

D (dd)7.22

-0.00

1.53

7.01

7.02

7.02

7.03

7.08

7.17

7.17

7.18

7.18

7.21

7.21

7.22

7.22

7.25

Figure S3. The 1H-NMR of b1

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5ppm

130916-24han jian hua 6in CDCl3 1H

1.00

1.04

0.99

A (d)6.91

B (d)6.97

C (s)6.99

0.00

1.53

2.17

6.90

6.91

6.97

6.98

6.99

7.26

Figure S4. The1H-NMR of b2

-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5ppm

150507-44HJH Thdabin CDCl3 1H

3.22

21.35

2.20

2.05

1.96

1.00

A (dd)7.22

B (m)6.92

C (m)2.63

D (dd)1.62

E (d)0.91

F (d)1.30

0.88

0.90

0.91

1.28

1.32

1.61

1.63

1.65

2.61

2.63

2.65

6.91

6.91

6.91

6.91

6.93

6.93

6.94

6.94

7.21

7.22

7.22

7.23

Figure S5. The 1H-NMR of c1

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0ppm

141223-23HJH TH2Brdadin CDCl3 1H

2.82

18.01

2.14

2.04

1.00

A (s)6.97

B (m)2.72

C (dd)1.76

D (d)1.12

E (d)1.52

1.11

1.13

1.14

1.50

1.53

1.54

1.75

1.76

1.78

2.70

2.72

2.74

6.97

-100102030405060708090100110120130140150160170180190200210ppm

141223-23HJH TH2Brdadin CDCl3 13C

A (s)14.32

B (s)22.91

C (s)29.33

D (m)29.78

E (s)32.13

F (s)108.09

G (s)110.49

H (s)130.89

I (s)142.90

14.32

22.91

29.33

29.59

29.63

29.76

29.87

29.90

29.95

32.13

108.09

110.49

130.89

142.90

Figure S6. The 1H-NMR and 13C-NMR of c2

FigureS7. The 1H-NMR of PDTH

Figure S8. The 1H-NMR of PDKZ(1,1,2,2-Tetrachloroethane-d2)

FigureS9. The 1H-NMR of PDKZ1T73(1,1,2,2-Tetrachloroethane-d2)

Figure S10. The 1H-NMR of PDKZ3T73(1,1,2,2-Tetrachloroethane-d2)

Figure S11. The 1H-NMR of PDTH2(1,1,2,2-Tetrachloroethane-d2)

Figure S12.The 1H-NMR of PDKZ(Entry 4 in DMSO-D6)

Figure S13. The 1H-NMR of PDKZ(Entry 5 in DMSO-D6)

Figure S14. The 1H-NMR of PDKZ1T73(Entry 7 in DMSO-D6)

Figure S15. The 1H-NMR of PDKZ3T73(Entry 8 in DMSO-D6)

Figure S16. The1H-NMR of PDTH2(Entry 9 in DMSO-D6)

Figure S17. The GPC curve of PDTH in entry 2

Figure S18. The GPC curves of PDKZ in entry 4

Figure S19. The GPC curves of PDKZ in entry 5

FigureS20. The GPC curves of PDKZ1T73 in entry 7

Figure S21. The GPC curves of PDKZ3T73 in entry 8

Figure S22. The GPC curves of PDTH2 in entry 9

3. HPLC-MS spectrum of polymerized products

Ⅰ: m/z=556

Ⅱ:m/z=637

Ⅲ：m/z=873

Figure S23. The HPLC-MS of entry 1(content: Ⅰ：36% Ⅱ ：22.8% Ⅲ：23%)

Figure S24. The HPLC-MS data of entry 2(In ethanol solution after Soxhlet extraction)

4. DSC and CV curves of polymers

160 180 200 220 240 260 280 300 320 340Tempreature(℃)

PPE-3Ex

othe

rm

Tg=260℃

Figure S25. The DSC curve of PDTH

Figure S26. The DSC curves of polymers

(a) (b)

(c) (d)

(e) (f)

The HOMO energy levels were calculated from cyclic voltammetry and were referenced to ferrocene (4.8 eV ; EFc/Fc+

1/2=0.12 V). EHOMO=-(EOxonset+4.8 eV- EFc/Fc+

1/2) eV;ELUMO=Egopt+EHOMO; Egopt was determined by onset wavelength of optical absorption.

Figure S27. The CV curves of polymers

Figure S28. The polymer fluorescence images