Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2019.

Supporting Information
for Adv. Mater., DOI: 10.1002/adma.201806010

Ambipolar Conjugated Polymers with Ultrahigh

Balanced Hole and Electron Mobility for Printed Organic
Complementary Logic via a Two-Step C-H Activation
Strategy
Zhenjie Ni, Hanlin Wang, Qiang Zhao, Jianqi Zhang, Zhixiang
Wei, Huanli Dong,* and Wenping Hu*
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2019.

Supporting Information for

Ambipolar Conjugated Polymers with Ultrahigh Balanced Hole and Electron Mobility
for Printed Organic Complementary Logic via a Two-Step C-H Activation Strategy

Zhenjie Ni, Hanlin Wang, Qiang Zhao, Jianqi Zhang, Zhixiang Wei, Huanli Dong,* Wenping
Hu*

Table of Contents
------------------
Part 1: General Considerations S2
Part 2: Preparation and Characterization of Monomers S3
Part 3: Polymerization Reactions S9
Part 4: Transistor fabrication and Characterization S20
Part 5: References S29
Part 6: NMR Spectra S30

S1
Part 1: General Considerations
Unless otherwise stated, all reactions were carried out in an atmosphere of dry argon using an
oven-dried (120 °C) glassware. The solvents were degassed and purified by usual methods.[1]
Toluene was distilled from lithium aluminum hydride. Acetone was refluxed over potassium
permanganate before being distilled. A fraction of petroleum distilled between 40-55°C was
used for column chromatography. N,N-Dimethylacetamide (99.5%, Extra Dry over Molecular
Sieve, AcroSeal®) and N-methyl-2-pyrrolidone (99.5%, Extra Dry over Molecular Sieve,
AcroSeal®) was purchased from Acros Oganics Co., t
Bu2MeP·HBF4, Pd2(dba)3,
Pd2(dba)3·CHCl3 and Pd(OAc)2 were purchased from Sigma-Aldrich Co. and were used as
received. CataCXium®C, P(o-anisyl)3 and P(o-Tol)3 were purchased from Strem Chemicals,
Inc. and were used as received. Flash chromatography was performed on silica gel (200-300
mesh) according to the protocol of Still, Khan and Mitra.[2] Both TLC plate and silica gel
were purchased from Qingdao Ocean Chemicals. 1H NMR spectra were recorded on either a
Bruker FOURIER 300 or advance 400 HD spectrometer as solutions in deuterochloroform
(CDCl3) or tetrachloroethane-d2 (C2D2Cl4), unless otherwise indicated. Chemicals shifts are
given in parts per million (δ units) downfield from tetramethylsilane using the residual solvent
signal (CHCl3 7.26, C2H2Cl4 6.00 or TMS 0.00) as internal standard. Proton (1H) NMR
information is given in the following format: multiplicity (s, singlet; d, doublet; t, triplet; q,
quartet; qui, quintet; sept, septet; m, multiplet), coupling constant(s) (J) in Hertz (Hz), number
of protons. The prefix app is occasionally applied when the true signal multiplicity was
unresolved and br indicates the signal in question is broadened. Carbon (13C) NMR spectra
are reported in ppm (δ) relative to residual CHCl3 (δ 77.16) or C2H2Cl4 (δ 73.78). High-
resolution mass spectra (HRMS) were performed at the Analytical Center of the Institute of
Chemistry, Chinese Academy of Science (ICCAS). Gel permeation chromatography (GPC)
was performed on Agilent G7820A PL-GPC220 at 120 oC using 1,2-dichlorobenzene as
eluent. OFET characteristics were carried out in ambient using a Keithley 4200
semiconductor characterization system. Inkjet-printing was carried out using a Microfab
Jetlab II inkjet-printer.

S2
Part 2: Preparation and Characterization and Substrates

2,5-Bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione[3]
To a solution of 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (7.0 g, 23.3
mmol) in DMF (150 ml) was added K2CO3 (9.7 g, 70.0 mmol) and heated to 120 °C for 1 h,
then 2-octyldodecylbromide (25.3 g, 70.0 mmol) was added dropwise. After being stirred for
another 2 h at 120 °C, the reaction mixture was poured into water and extracted with
chloroform. The combined organic layers were washed with water, dried over Na2SO4, and
concentrated in vacuum. The residue was purified by column chromatography over silica gel
using a mixture of petroleum ether and dichloromethane as eluent. Finally, the result product
was recrystallized from ethanol.
38% yield; purple solid; TLC (PE: DCM, 5:1 v/v): Rf = 0.20; 1H NMR (400 MHz, CDCl3): δ
8.88 (d, J = 3.2 Hz, 2H), 7.63 (d, J = 4.8 Hz, 2H), 7.28 (t, J = 4.4 Hz, 2H), 4.03 (d, J = 7.6 Hz,
4H), 1.92, (br s, 2H), 1.31-1.22 (m, 64H), 0.90-0.85 (m, 12H).

3-(5-Bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-
1,4(2H,5H)-dione[4]
2,5-Bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (1.72 g,
2 mmol) was dissolved in chloroform (30 mL) and stirred at room temperature, then N-
bromosuccinimide (0.32 g, 1.8 mmol) was added in small portion for 30 min. After being
stirred overnight, the solvent was concentrated in vacuum. The residue was purified by
column chromatography over silica gel using a mixture of petroleum ether and
dichloromethane as eluent.
54% yield; purple solid; TLC (PE: DCM, 5:1 v/v): Rf = 0.30; 1H NMR (300 MHz, CDCl3): δ
8.88 (dd, J = 0.9, 3.9 Hz, 1H), 8.61 (d, J = 4.2 Hz, 1H), 7.63 (dd, J = 0.9, 5.0 Hz, 1H),7.28-

S3
7.24 (m, 1H), 7.22 (d, J = 4.2 Hz, 1H), 4.01 (d, J = 7.7 Hz, 2H), 3.93 (d, J = 7.7 Hz, 2H), 1.89
(br s, 2H), 1.29-1.22 (m, 64H), 0.93-0.81 (m, 12H).

3,6-Bis(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-
dione[3]
2,5-Bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (1.72 g,
2 mmol) was dissolved in chloroform (30 mL) and stirred at room temperature, then N-
bromosuccinimide (0.78 g, 4.4 mmol) was added in small portion for 30 min. After being
stirred overnight, the solvent was concentrated in vacuum. The residue was purified by
column chromatography over silica gel using a mixture of petroleum ether and
dichloromethane as eluent.
83% yield; dark purple solid; TLC (PE: DCM, 5:1 v/v): Rf = 0.35; 1H NMR (400 MHz,
CDCl3): δ 8.62 (d, J = 4.2 Hz, 2H), 7.21 (d, J = 4.2 Hz, 2H), 3.91 (d, J = 7.7 Hz, 4H), 1.87 (br
s, 2H), 1.28-1.22 (m, 64H), 0.89-0.84 (m, 12H).

4,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[c][1,2,5]thiadiazole[5]
4,7-Dibromobenzo[c][1,2,5]thiadiazole (588 mg, 2.0 mmol), bis(pinacolato)diboron (1.27 g,
5.0 mmol), and potassium acetate (980 mg, 10.0 mmol) were dissolved in dry 1,4-dioxane (20
mL), and then [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (146 mg, 0.20 mmol)
was added and the reaction mixture was heated with stirring at 80 oC for 24 h. After cooling to
room temperature, the mixture was poured into water and then extracted ethyl acetate (3×50
mL). The combined organic layers were washed with brine, dried over Na2SO4, and
concentrated in vacuum. The crude product was purified by column chromatography over
silica gel using a mixture of petroleum ether and dichloromethane as eluent.
49% yield; yellow solid; TLC (PE: DCM, 1:1 v/v): Rf = 0.25;
1
H NMR (300 MHz, CDCl3): δ 8.12 (s, 2H), 1.43 (s, 24H).

S4
6,6'-(5,5'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-
octyldodecyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DBD)
Pathway (a):
3-(5-Bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-
1,4(2H,5H)-dione (470 mg, 0.5 mmol) and 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)benzo[c][1,2,5]thiadiazole (78 mg, 0.2 mmol) in toluene were dissolved in toluene (5 mL)
under an argon atmosphere. Pd(PPh3)4 (11.6 mg, 0.01 mmol), K2CO3 (aq. 2M, 1 mL) and two
drops of aliquat 336 were then added, the mixture was stirring at 100 ºC for 48 h. The cooled
mixture was diluted with water (50 mL) and extracted with dichloromethane (3 × 50 mL). The
combined organic layers were washed with brine, dried over Na2SO4, and concentrated in
vacuum. The residue was purified by column chromatography over silica gel.
79% yield; black solid; TLC (PE: DCM, 2:1 v/v): Rf = 0.20;
1
H NMR (300 MHz, tetrachloroethane-d2): δ 9.08 (d, J = 4.2 Hz, 2H), 8.91 (d, J = 3.4 Hz,
2H), 8.16 (d, J = 4.2 Hz, 2H), 8.02 (s, 2H), 7.66 (d, J = 5.0 Hz, 2H), 7.33-7.25 (m, 2H), 4.13
(d, J = 5.2 Hz, 4H), 4.03 (d, J = 6.0 Hz, 4H), 2.03 (br s, 2H), 1.92 (br s, 2H), 1.38-1.11 (m,
128H), 0.87-0.77 (m, 24H);
13
C NMR (75 MHz, tetrachloroethane-d2): δ 161.46, 161.36, 152.00, 143.77, 140.12, 139.67,
136.20, 135.29, 131.42, 130.83, 129.64, 128.34, 127.89, 125.72, 125.42, 108.49, 108.06,
46.13, 37.96, 37.57, 31.76, 31.24, 31.08, 30.04, 29.92, 29.54, 29.47, 29.40, 29.25, 26.25,
26.10, 22.59, 14.11;
HRMS (MALDI-TOF) calcd. for C114H177N6O4S5+ ([M+H]+): 1854.2429, found 1854.2427.
Pathway (b):
2,5-Bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (344
mg, 0.4 mmol) and 4,7-dibromobenzo[c][1,2,5]thiadiazole (44 mg, 0.15 mmol) were

S5
dissolved in dry NMP (3 mL) under an argon atmosphere. Pd(OAc)2 (3.4 mg, 0.015 mmol)
and PivOH (40.8 mg, 0.4 mmol) and K2CO3 (165.6 mg, 1.2 mmol) were then added, the
reaction mixture was stirring at 120 ºC for 24 h. The cooled mixture was diluted with water
(30 mL) and extracted with dichloromethane (3 × 30 mL). The combined organic layers were
washed with brine, dried over Na2SO4, and concentrated in vacuum. The residue was purified
by column chromatography over silica gel.
43% yield; black solid; TLC (PE: DCM, 2:1 v/v): Rf = 0.20;
1
H NMR (300 MHz, tetrachloroethane-d2): δ 9.08 (d, J = 4.2 Hz, 2H), 8.91 (d, J = 3.4 Hz,
2H), 8.16 (d, J = 4.2 Hz, 2H), 8.02 (s, 2H), 7.66 (d, J = 5.0 Hz, 2H), 7.33-7.25 (m, 2H), 4.13
(d, J = 5.2 Hz, 4H), 4.03 (d, J = 6.0 Hz, 4H), 2.03 (br s, 2H), 1.92 (br s, 2H), 1.38-1.11 (m,
128H), 0.87-0.77 (m, 24H);
13
C NMR (75 MHz, tetrachloroethane-d2): δ 161.46, 161.36, 152.00, 143.77, 140.12, 139.67,
136.20, 135.29, 131.42, 130.83, 129.64, 128.34, 127.89, 125.72, 125.42, 108.49, 108.06,
46.13, 37.96, 37.57, 31.76, 31.24, 31.08, 30.04, 29.92, 29.54, 29.47, 29.40, 29.25, 26.25,
26.10, 22.59, 14.11;
HRMS (MALDI-TOF) calcd. for C114H177N6O4S5+ ([M+H]+): 1854.2429, found 1854.2427.

6,6'-(5,5'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-5,2-diyl))bis(3-(5-
bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)
(BrDBD)
6,6'-(5,5'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-
octyldodecyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (1.11 g, 0.6 mmol)
was dissolved in chloroform (30 mL) and stirred at room temperature, then N-
bromosuccinimide (235 mg, 1.32 mmol) was added in small portion for 10 min under an
argon atmosphere. After being stirred overnight, the solvent was concentrated in vacuum. The
residue was purified by column chromatography over silica gel using a mixture of petroleum
ether and dichloromethane as eluent.
78% yield; black solid; TLC (PE: DCM, 2:1 v/v): Rf = 0.25;

S6
1
H NMR (400 MHz, CDCl3): δ 9.04 (d, J = 3.9 Hz, 2H), 8.65 (d, J = 3.9 Hz, 2H), 8.02 (d, J =
4.0 Hz, 2H), 7.77 (s, 2H), 7.12 (d, J = 4.1 Hz, 2H), 4.04 (d, J = 6.9 Hz, 4H), 4.91 (d, J = 6.9
Hz, 4H), 1.98 (br s, 2H), 1.89 (br s, 2H), 1.37-1.19 (m, 128H), 0.86-0.81 (m, 24H);
13
C NMR (100 MHz, CDCl3): δ 161.32, 161.07, 151.96, 143.95, 139.94, 136.49, 135.36,
131.69, 130.32, 127.93, 125.31, 118.76, 108.35, 108.30, 46.50, 46.40, 38.21, 37.85, 31.91,
31.24, 30.22, 30.07, 29.74, 29.67, 29.63, 29.56, 29.38, 29.34, 26.37, 26.26, 22.68, 14.10;
HRMS (MALDI-TOF) calcd. for C114H175Br2N6O4S5+ ([M+H]+): 2010.0640, found
2010.0638.

2,5-Dibromothiophene
Thiophene (1.68 g, 20 mmol) was dissolved in dry DMF (15 mL) at room temperature, then
N-bromosuccinimide (8.54 g, 48 mmol) was added in small portions for 30 min. After being
stirred overnight, the solvent was concentrated in vacuum. The residue was purified by
column chromatography over silica gel using hexane as eluent.
61% yield; colorless oil; TLC (Hexane): Rf = 0.80;
1
H NMR (400 MHz, CDCl3): δ 6.84 (s, 2H).

2,5-Dibromoselenophene
Selenophene (2.62 g, 20 mmol) was dissolved in dry DMF (15 mL) at room temperature, then
N-bromosuccinimide (8.54 g, 48 mmol) was added in small portions for 30 min. After being
stirred overnight, the solvent was concentrated in vacuum. The residue was purified by
column chromatography over silica gel using hexane as eluent.
58% yield; pale yellow oil; TLC (Hexane): Rf = 0.80;
1
H NMR (400 MHz, CDCl3): δ 7.00 (s, 2H).

2,5-Bis(trimethylstannyl)thiophene[6]
To a solution of thiophene (0.84 g, 10 mmol) and TMEDA (2.33 g, 20 mmol) in hexane (50
ml) was added nBuLi (2.0 M in hexane) (11 ml, 22 mmol) at -20 °C under argon. The
resulting mixture was heated to reflux for 30 min, after cooling to -20 °C trimethyltin chloride
solution (1.0 M in hexane) (25 ml, 25 mmol) was then added dropwise and the solution stirred

S7
at room temperature for 15 h. The reaction mixture was quenched with a saturated solution of
ammonium chloride and extracted with diethyl ether. The organic layer was washed with
brine, dried over Na2SO4 and concentrated in vacuum. The residue was recrystallized from
methanol.
79% yield; White crystals; 1H NMR (300 MHz, CDCl3): δ 7.38 (s, 2 H), 0.38 (m, 18 H).

2,5-Bis(trimethylstannyl)selenophene[7]
To a solution of selenophene (1.31 g, 10 mmol) in THF (50 ml) was added nBuLi (2.0 M in
hexane) (11 ml, 22 mmol) at -78 °C under argon. The resulting mixture was stirred at room
temperature for 30 min. The solution was cooled again to -78 °C and trimethyltin chloride
solution (1.0 M in hexane) (25 ml, 25 mmol) was then added dropwise and the solution was
allowed to warm to room temperature. The reaction mixture was poured into water and
extracted with diethyl ether. The organic layer was washed with brine, dried over Na2SO4 and
concentrated in vacuum. The residue was recrystallized from methanol.
86% yield; White crystals; 1H NMR (300 MHz, CDCl3): δ 7.68 (s, 2 H), 0.37 (m, 18 H).

S8
Part 3: Polymerization Reaction

Figure S1. (a) A Five-step, conventional synthetic procedures of PDBD-T and PDBD-Se. (b)
An all C-H activation route with simplified steps for PDBD-T and PDBD-Se.

S9
Table S1. Optimization of reaction conditions for key intermediate DBD.a

Batch Catalyst Ligand Solvent Yield

(5 mol %) (10 mol %) (%)
-
1 Pd(OAc)2 DMF 30
t
2 Pd(OAc)2 Bu2MeP·HBF4 DMF 21
-
3 Pd(OPiv)2 DMF 26
-
4 Pd(OAc)2 DMAc 32
5 Pd(OAc)2 - NMP 43
a
Reaction conditions: 1 (0.4 mmol), 2 (0.15 mmol), K2CO3 (1.2 mmol), PivOH (0.4 mmol) in degassed solvent (3 mL) at
120 °C for 24 h. Isolated yield.

S10
Table S2. Optimization of the C-H Activation Polymerization for PDBD-T.a

Batch Catalyst Ligand Base Solvent Mn Ɖ Yield

(2 mol %) (6 mol %) (KDa) (%)
b t
1 Pd(OAc)2 Bu2MeP·HBF4 K2CO3 DMAc 33.9 1.72 45
2 Pd2(dba)3 - K2CO3 Toluene - - -
c
3 Pd2(dba)3·CHCl3 P(o-anisyl)3 Cs2CO3 2MeTHF 29.4 1.61 32
4 H-B cat. P(o-anisyl)3 Cs2CO3 Toluene 73.9 1.52 61
Stille Pd2(dba)3 P(o-Tol)3 - Toluene/NMP 109.1 1.86 98
Polymerization
a
Reaction conditions: DBD (0.1 mmol), 2,5-dibromothiophene (0.1 mmol), base (3 equiv), acid additive (1 equiv) in degassed
toluene (0.1 M ) at 110 °C for 24 h. Isolated yields after Soxhlet extraction. Number-average molar mass (Mn) and dispersity
(Ɖ) was determined by GPC at 140 °C in 1,2-dichlorobenzene. bReaction conditions: catalyst (3 mol%) and ligand (6 mol%)
in DMAc at 120 °C for 24h. cReaction carried out at 85 °C.

S11
Polymerization for PDBD-T
Under an argon atmosphere, a mixture of DBD (185.5 mg, 0.10 mmol), 2,5-dibromothiophene
(24.2 mg, 0.10 mmol), Herrmann-Beller catalyst (1.9 mg, 0.002 mmol, 2 mol %), P(o-anisyl)3
(2.1 mg, 0.06 mmol, 6 mol%), PivOH (10.2 mg, 0.10 mmol), and Cs2CO3 (97.7 mg, 0.30
mmol) were dissolved in degassed toluene (1.0 mL) in a Schlenk tube. The reaction was
stirred at room temperature for 5 min and then heated to 110 °C with rotating speed of 450
rpm for 24 h. After cooling to room temperature, the mixture was precipitated into chilled
methanol (100 mL). Then the crude polymer was collected by filtration and purified by
Soxhlet extraction with acetone and heptane. The remaining product was dissolved with
refluxing 1,1,2,2-tetrachloroethane. The tetrachloroethane solution was then concentrated by
evaporation and precipitated into methanol, dried over vacuum. Finally, the desired polymer
was obtained.
61% yield; GPC(1,2-dichlorobenzene, 140 °C): Mn = 73.9 KDa, Mw= 112.6 KDa, Ɖ = 1.52;
Anal. Calcd. for C118H176N6O4S6, C, 73.24; H, 9.17; N, 4.34; Found: C, 73.14; H, 9.17; N,
4.33.

Polymerization for PDBD-T (via Stille polymerization)

Under an argon atmosphere, 2,5-bis(trimethylstannyl)thiophene (41.0 mg, 0.10 mmol),
BrDBD (201.3 mg, 0.10 mmol), Pd2(dba)3 (2.7 mg, 0.003 mmol, 3 mol %) and P(o-Tol)3 (2.7
mg, 0.009 mmol, 9 mol %) were dissolved in degassed toluene/NMP (5/1 V/V, 7.2 mL) in a
Schlenk tube. The reaction was stirred at 110 °C with rotating speed of 450 rpm for 6 h,
followed by addition of 2-bromothiophene (1.0 mL) to react with the trimethylstannyl end
group. The mixture was further stirred at 100 °C for 1 h. After cooling to room temperature,
the mixture was precipitated into chilled methanol (40 mL). Then the crude polymer was

S12
collected by filtration and purified by Soxhlet extraction with acetone and heptane. The
remaining product was dissolved with refluxing 1,1,2,2-tetrachloroethane. The
tetrachloroethane solution was then concentrated by evaporation and precipitated into
methanol, dried over vacuum. Finally, the desired polymer was obtained.
98% yield; GPC(1,2-dichlorobenzene, 140 °C): Mn = 109.1 KDa, Mw= 202.9 KDa, Ɖ = 1.86;
Anal. Calcd. for C118H176N6O4S6, C, 73.24; H, 9.17; N, 4.34; Found: C, 73.07; H, 9.20; N,
4.34.

1
H NMR of PDBD-T (tetrachloroethane-d2, 373K):

S13
GPC measurement of PDBD-T

S14
GPC measurement of PDBD-T (via Stille polymerization)

S15
Polymerization for PDBD-Se
Under an argon atmosphere, a mixture of DBD 3 (185.5 mg, 0.10 mmol), 2,5-
dibromoselenophene (28.9 mg, 0.10 mmol), Herrmann-Beller catalyst (1.9 mg, 0.002 mmol, 2
mol %), P(o-anisyl)3 (2.1 mg, 0.06 mmol, 6 mol%), PivOH (10.2 mg, 0.10 mmol), and
Cs2CO3 (97.7 mg, 0.30 mmol) were dissolved in degassed toluene (1.0 mL) in a Schlenk tube.
The reaction was stirred at room temperature for 5 min and then heated to 110 °C with
rotating speed of 450 rpm for 24 h. After cooling to room temperature, the mixture was
precipitated into chilled methanol (100 mL). Then the crude polymer was collected by
filtration and purified by Soxhlet extraction with acetone and heptane. The remaining product
was dissolved with refluxing 1,1,2,2-tetrachloroethane. The tetrachloroethane solution was
then concentrated by evaporation and precipitated into methanol, dried over vacuum. Finally,
the desired polymer was obtained.
53% yield; GPC(1,2-dichlorobenzene, 140 °C): Mn = 64.6 KDa, Mw= 109.6 KDa, Ɖ = 1.70;
Anal. Calcd. for C118H176N6O4S5Se, C, 71.51; H, 8.95; N, 4.24; Found: C, 71.19; H, 8.78; N,
4.20.

Polymerization for PDBD-Se (via Stille polymerization)

Under an argon atmosphere, 2,5-bis(trimethylstannyl)selenophene (45.7 mg, 0.10 mmol),
BrDBD (201.3 mg, 0.10 mmol), Pd2(dba)3 (2.7 mg, 0.003 mmol, 3 mol %) and P(o-Tol)3 (2.7
mg, 0.009 mmol, 9 mol %) were dissolved in degassed toluene/NMP (5/1 V/V, 7.2 mL) in a
Schlenk tube. The reaction was stirred at 110 °C with rotating speed of 450 rpm for 6 h,
followed by addition of 2-bromothiophene (1.0 mL) to react with the trimethylstannyl end
group. The mixture was further stirred at 100 °C for 1 h. After cooling to room temperature,
the mixture was precipitated into chilled methanol (40 mL). Then the crude polymer was

S16
collected by filtration and purified by Soxhlet extraction with acetone and heptane. The
remaining product was dissolved with refluxing 1,1,2,2-tetrachloroethane. The
tetrachloroethane solution was then concentrated by evaporation and precipitated into
methanol, dried over vacuum. Finally, the desired polymer was obtained.
93% yield; GPC(1,2-dichlorobenzene, 140 °C): Mn = 96.5 KDa, Mw= 203.2 KDa, Ɖ = 2.11;
Anal. Calcd. for C118H176N6O4S5Se, C, 71.51; H, 8.95; N, 4.24; Found: C, 71.17; H, 9.03; N,
4.19.

1
H NMR of PDBD-Se (tetrachloroethane-d2, 373K):

S17
GPC measurement of PDBD-Se

S18
GPC measurement of PDBD-Se (via Stille polymerization)

S19
Part 4: Transistor fabrication and characterization

Fabrication of OFET devices

To evaluate the polymer semiconductors, a top gate, bottom contact configuration was used.
188 µm thick polyethylene terephthalate (PET) substrates were rinsed with deionized water,
ethanol, acetone, then dried by nitrogen before device fabrication. Next, 20 nm gold
interdigitated fingers (channel width 4500 µm, channel length 90 µm) were deposited by
thermal-evaporation. All polymers were dissolved in 1,2-dichlorobenzene (o-DCB) with a
concentration of 4 mg mL−1. The polymer solution was spin-coated on PET at a speed of 1800
rpm and dried at 140 °C for 10 minutes on a hotplate. Polymethyl methacrylate (PMMA)
dissolved in n-butyl acetate (60 mg mL−1) served as the dielectric and dried at 90 °C for 10
minutes. To complete the fabrication, 50 nm thick aluminium was thermally-deposited
through shadow mask as gate contact. OFET characteristics were carried out in ambient using
a Keithley 4200 semiconductor characterization system. The carrier mobility in saturation
region (μ) was calculated according to the equation:
IDS = Ciμ(W/2L)(VGVT)2
where IDS is the drain current; Ci is the capacitance per unit area of the gate dielectric layer; W
and L are the semiconductor channel width and length, respecitively; and VT and VG are the
threshold voltage and the gate voltage, respectively.
The PMMA thickness used in this research is measured to be 900 to 950 nm by a XP2 profiler.
PMMA is known to possess a relative dielectric constant of 3.6, thus PMMA dielectric can be
roughly estimated by:
Ci= ε0εr/d = 3.35-3.54 nF cm−2.

S20
Figure S2. (a) UV-Vis absorption spectrum of PDBD-T and PDBD-Se in thin fim state. (b)
Secondary electron cut-off spectra of PDBD-T and PDBD-Se. (c) Valence region spectra of
PDBD-T and PDBD-Se.

Figure S3. TGA plot of PDBD-T (a) and PDBD-Se (b) with a heating rate of 10 ºC min-1
under nitrogen atmosphere.

S21
Figure S4. UV-Vis absorption spectrum of PDPP-T, PDPP-Se and PDPP-Btz.

Figure S5. UPS data. (a) Secondary electron cut-off spectra of PDPP-T, PDPP-Se and PDPP-
Btz. (b) Valence region spectra of PDPP-T, PDPP-Se and PDPP-Btz.

S22
Figure S6. (a) A typical p-type transfer characteristics of PDPP-T. (b) A typical p-type output
characteristics of PDPP-T.

Figure S7. (a) A typical p-type transfer characteristics of PDPP-Se. (b) A typical p-type
output characteristics of PDPP-Se.

S23
Figure S8. (a) The p-type transfer curve of PDBD-Se shows a hole mobility of 8.90 cm2 V−1
s−1. (b) The n-type transfer curve indicates an electron mobility of 7.71 cm2 V−1 s−1 in PDBD-
Se.

S24
Figure S9. (a-b) PDBD-Se’s hole and electron mobility are plotted as a function of V G
(calculated from the VOnset). (c-d) PDBD-T’s hole and electron mobility are plotted as a
function of VG (calculated from the VOnset). Reliability factor, r is calculated according to Ref.
8, which is 63%/68% for PDBD-T’s hole/electron mobility and 71%/75% for PDBD-Se’s
hole/electron mobility.

S25
Figure S10. Bias stress (VG = 80 V for 3600 s) leads to a positive shift in PDBD-Se’s n-type
transfer curve with a ΔVG of 7 V.

S26
Figure S11. (a-b) Typical p-type and n-type transfer curves of PDPP-Btz. (c-d) Typical p-
type and n-type output curves of PDPP-Btz.

S27
Figure S12. (a-b) Typical p-type and n-type transfer curves of PDBD-Se inkjet-printed with
mesitylene. Its p-/n-type mobility extracted to be 4.73/2.55 cm2 V−1 s−1, respectively.

S28
Part 5: References
[1] W. L. Armarego, C. L. L. Chai, Purification of laboratory chemicals; Butterworth-
Heinemann, 2013.
[2] W. C. Still, M. Kahn, A. Mitra, J. Org. Chem. 1978, 43, 2923.
[3] Y. Li, S. P. Singh, P. Sonar, Adv. Mater. 2010, 22, 4862.
[4] D. Yoo, B. Nketia‐ Yawson, S. J. Kang, H. Ahn, T. J. Shin, Y. Y. Noh, C. Yang, Adv.
Funct. Mater. 2015, 25, 586.
[5] M. Zhang, H. N. Tsao, W. Pisula, C. Yang, A. K. Mishra, K. Müllen, J. Am. Chem.
Soc. 2007, 129, 3472.
[6] J. Linshoeft, A. C. J. Heinrich, S. A. W. Segler, P. J. Gates, A. Staubitz, Org. Lett.
2012, 14, 5644.
[7] X. Zhang, J. Yao, C. Zhan, Chem. Commun. 2015, 51, 1058.
[8] H. H. Choi, K. Cho, C. D. Frisbie, H. Sirringhaus, V. Podzorov, Nat. Mater. 2018, 17,
2.

S29
Part 6: NMR Spectra
1
H NMR (300 MHz, CDCl3) of 2,5-bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-
c]pyrrole- 1,4(2H,5H)-dione

1
H NMR of 3-(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)-6-(thiophen-2-yl)pyrrolo[3,4-
c] pyrrole-1,4(2H,5H)-dione

1
H NMR of 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[c][1,2,5]thiadiazole

S30
1
H NMR (300 MHz, CDCl3) of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-
octyldodecyl)pyrrolo[3,4 -c]pyrrole-1,4(2H,5H)-dione

S31
1
H NMR (300 MHz, tetrachloroethane-d2) of DBD

13
C NMR (75 MHz, tetrachloroethane-d2) of DBD

S32
1
H NMR (400 MHz, CDCl3) of BrDBD

13
C NMR (100 MHz, CDCl3) of BrDBD

S33
1
H NMR (400 MHz, CDCl3) of 2,5-dibromothiophene

1
H NMR (400 MHz, CDCl3) of 2,5-dibromoselenophene

S34
1
H NMR of 2,5-bis(trimethylstannyl)thiophene

1
H NMR of 2,5-bis(trimethylstannyl)selenophene

S35