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Supporting Information Significant Improvement of Unipolar n-Type Transistor Performances by Manipulating the Coplanar Backbone Conformation of Electron-Deficient Polymers via Hydrogen-Bonding Yang Wang*, Tsukasa Hasegawa, Hidetoshi Matsumoto, and Tsuyoshi Michinobu*

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(1) General measurements

Nuclear magnetic resonance (NMR) spectra were recorded using a JEOL model

AL300 (300 MHz) at room temperature. Deuterated chloroform or deuterated

1,1,2,2-tetrachloroethane was used as the solvent. The NMR chemical shifts were

reported in ppm (parts per million) relative to the residual solvent peak at 7.26 ppm

(chloroform) or 6.00 ppm (1,1,2,2-tetrachloroethane) for the 1H NMR spectroscopy

and 77.6 ppm (chloroform) or 73.8 ppm (1,1,2,2-tetrachloroethane) for the 13C NMR

spectroscopy. Coupling constants (J) were given in Hz. The resonance multiplicity

was described as s (singlet), d (doublet), t (triplet), and m (multiplet). Fourier

transform infrared (FT-IR) spectra were recorded by a JASCO FT/IR-4100

spectrometer in the range from 4000 to 600 cm−1. The MALDI−TOF mass spectra

were measured by a Shimadzu/Kratos AXIMACFR mass spectrometer equipped with

a nitrogen laser (λ = 337 nm) and pulsed ion extraction, which was operated in the

linear-positive ion mode at an accelerating potential of 20 kV. CHCl3 solutions

containing 1 g L-1 of a sample, 10 g L-1 of dithranol, and 1 g L-1 of sodium

trifluoroacetate were mixed at a ratio of 1:1:1, then 1 μL aliquot of this mixture was

deposited onto a sample target plate. Gel permeation chromatography (GPC) was

measured by a JASCO GULLIVER 1500 equipped with a pump (PU-2080 Plus), an

absorbance detector (RI-2031 Plus), and two Shodex GPC KF-803 columns (8.0 mm

I.D. × 300 mm L) based on a conventional calibration curve using polystyrene

standards. o-Dichlorobenzene (40 °C) was used as the carrier solvent at the flow rate

of 0.5 mL min−1. The molecular weights were calculated based on a conventional

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calibration curve using polystyrene standards. The UV-vis-NIR spectra were recorded

by a JASCO V-670 spectrophotometer. Thermogravimetric analysis (TGA) and

differential scanning calorimetry (DSC) measurements were carried out using a

Rigaku TG8120 and a Rigaku DSC8230, respectively, under flowing nitrogen at the

scan rate of 10 °C min−1.

The electrochemical measurements were carried out using a BAS electrochemical

analyzer model 612C at 25 °C in a classical three-electrode cell. The working,

reference, and auxiliary electrodes were a glassy carbon electrode,

Ag/AgCl/CH3CN/nBu4NPF6, and a Pt wire, respectively. The polymer films for the

electrochemical measurements were coated from a CHCl3 solution (ca. 3 g L−1). For

calibration, the redox potential of ferrocene/ferrocenium (Fc/Fc+) was measured under

the same conditions, and it was located at 0.07 V vs. the Ag/AgCl electrode. It was

assumed that the redox potential of Fc/Fc+ has an absolute energy level of −4.80 eV to

a vacuum. The HOMO and LUMO energy levels were then calculated according to

the following equations:

EHOMO = −(φox + 4.73) (eV) (Eq. 1)

ELUMO = −(φre + 4.73) (eV) (Eq. 2)

where φox is the onset oxidation potential vs. Ag/AgCl and φre is the onset reduction

potential vs. Ag/AgCl.

(2) Fabrication and characterization of organic transistors

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Top-contact/bottom-gate (TC/BG) PTFT-devices were fabricated on n+-Si/SiO2

substrates in which n+-Si and SiO2 were used as the gate electrode and gate dielectric,

respectively. The substrates were subjected to cleaning and modified with

octadecyltrimethoxysilane (OTMS) or

[3-(N,N-dimethylamino)propyl]trimethoxysilane (NTMS) to form a self-assembled

monolayer (SAM) according to the literature.S1 Thin films of the polymers were

deposited on the treated substrate by spin-coating the polymer solutions inside an

argon-filled glovebox followed by thermal annealing. The details of the thermal

annealing conditions were 200 or 250 oC for 10 min in an Ar-filled glovebox. After

the polymer thin film deposition, ~50 nm thick gold was deposited as the source and

drain contacts using a shadow mask. The PTFT devices had a channel length (L) of

100 μm and a channel width (W) of 1 mm. The PTFT performances were measured

under vacuum (10−4 mbar) using a Keithley 4200 parameter analyzer on a probe stage.

The carrier mobilities, μ, were calculated from the data in the saturated regime

according to the following equation:

ISD = (W/2L)Ciμ(VGS – VT)2

where ISD is the drain current in the saturated regime, W and L are the semiconductor

channel width and length, respectively, Ci (Ci = 13.7 nF cm−2) is the capacitance per

unit area of the gate dielectric layer, and VGS and VT are the gate voltage and

threshold voltage, respectively. VGS−VT of the devices was determined from the

square root values of ISD at the saturated regime.

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(3) Two-dimensional grazing-incidence wide-angle X-ray scattering

(2D-GIWAXS) measurements

2D-GIWAXS measurements were carried out at BL40B2 in SPring-8 (Hyogo, Japan).

The wavelength of the X-ray beam was 0.8 Å and the camera length was 341 mm.

The 2D-scattering images were acquired using a photon counting detector (Pilatus3X

2M, Dectris, Ltd.). The samples were mounted in a helium cell to reduce the radiation

damage. The data acquisition time was 10 s. The GIWAXS data were measured at the

incident angle of 0.10o, which was lower than the critical angle of the total external

reflection at the silicon surface and was close to those of the samples. The

components of the scattering vector, q, parallel and perpendicular to the sample

surface were defined as qxy and qz, respectively. Thin film samples for the GIWAXS

measurements were prepared in the same way as those of the PTFTs.

(4) Atomic force microscopy (AFM) measurements

The AFM samples were prepared by spin-coating the polymer solutions on a Si/SiO2

substrate. Both the pristine and thermally-treated films were analyzed by a Seiko

Instruments SPA-400 with a Seiko Instruments DF-20 stiff cantilever.

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(5) Supporting Figures

SN

NS

O

O SN

NS

O

O n

C10H21

C12H25

C10H21

C12H25

C10H21

C12H25

C10H21

C12H25

N

NS

NN

NS

N

S

S

C12H25C10H21

C12H25

C10H21

nS

N

S

O OC8H17

C10H21

S

N

S

O OC8H17

C10H21

S

FF

n

s-BTI2-FT

n

n

Donor Acceptor

Donor Acceptor Acceptor

N SN

PBPTV

hole/electron mobility 6.87/8.94 cm2 V-1 s-1

Reference: Y. Liu et al, J. Am. Chem. Soc.,2017, 139, 17735.

DPP-2T-DPP-TBT


Reference: Y. Liu et al, Adv. Mater.,2018, 30, 1801951.

unipolar electron mobility 0.82 cm2 V-1 s-1

Reference: X. Guo et al, Angew. Chem. Int. Ed.,2017, 56, 15304.

n

Donor Acceptor1 Acceptor2Donor

dual-acceptor strategy

S

NS

N

S

n

N

N

O

O

O

O

C10H21

C12H25

C10H21

C12H25

NN

N

C2H5

C4H9

Se

NS

N

Se

n

N

N

O

O

O

O

C10H21

C12H25

C10H21

C12H25


Reference: Y. Liu et al, Adv. Mater.,2017, 29, 1602410.

PNBS

unipolar electron mobility 5.35 cm2 V-1 s-1

Reference: Y. Wang et al, Adv. Mater.,2018, 30, 1707164.

25o

40o

NN O

NN

O

n

O

O

O

O

S

NS

N

S

C18H37

C18H37

C18H37

C18H37


Reference: G. Yu et al, Adv. Mater.,2018, 30, 1705286.

pSNT

Figure S1. (top) Schematic illustration of the dual-acceptor strategy (“D-A-A” or

“D-A1-D-A2” backbone strategy). (bottom) Chemical structures of the

high-performance ambipolar/n-type semiconducting polymers using the dual-acceptor

strategy in the literature. Among them, PBPTV and pSNT had a relatively large

dihedral angle (θ) of 25° and 40°, respectively.

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Figure S2. (a) Chemical structures of the high-performance semiconducting polymers

based on vinylene groups. (b) Synthetic difficulty in producing the key

vinylene-incorporated acceptor unit of

1,2-bis(7-bromobenzo[c][1,2,5]thiadiazol-4-yl)ethene by the one-pot Stille coupling

between 4,7-dibromobenzo[c][1,2,5]thiadiazole and 1,2-bis(tributylstannyl)ethene. (c)

Chemical structures of the low-performance semiconducting polymers containing the

vinylene spacers.

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Figure S3. GPC curves of (a) P1, (b) P2, (c) P3, and (d) P4 (eluent:

o-dichlorobenzene at 40 oC).

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Figure S4. (a) Thermogravimetric analysis (TGA) of the polymers under nitrogen

flow (50 mL min−1) at the heating rate of 10 °C min−1. (b to e) Differential scanning

calorimetry (DSC) curves of (b) P1, (c) P2, (d) P3, and (e) P4 under nitrogen flow

(50 mL min−1) at the scan rate of 10 °C min−1.

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Figure S5. UV-vis-NIR absorption profiles of the polymers in dilute chloroform

solutions.

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Figure S6. The molecular geometry of (a) P1; (b) P2; (c) P3 without side chains on

the thiophene units and (d) P4 without vinylene groups (the same as pSNT) optimized

at the B3LYP/6-31G(d) level of theory. The optimal dihedral angle (in degrees)

between the NDI and adjacent thiophene rings was indicated in the side view.

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Figure S7. I–V characteristics of the P3 and P4-based transistors with the

OTMS-modified SiO2/Si substrate under p-channel operating conditions (sweeping

from VGS = 20 to −80 V under VDS = −60 V).

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Figure S8. The measurement reliability factor (γ) is the ratio, expressed in %, of the

slopes of the black (theoretical assumption) and green dashed lines (linear fit for

mobility extraction) for the OTMS-treated PTFTs based on (a) P1; (b) P2; (c) P3; (d)

P4; and the NTMS-treated PTFTs based on (e) P3; (f) P4.

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Figure S9. Electron mobility changes as a function of gate voltages. The electron

mobilities were calculated from the local slope of the square root of the transfer curve

(Figure 3f) at the saturation regime (IDS1/2 versus VGS).

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Figure S10. I–V characteristics of the P3 and P4-based transistors with the

NTMS-modified SiO2/Si substrate under p-type operating conditions (sweeping from

VGS = 20 to −100 V under VDS = −60 V).

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Figure S11. Illustration of polymer backbone packing orientations and the charge

transport in bimodal orientation.

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Figure S12. AFM topography image of the thin film of (a) P1 and (b) the

corresponding 3D profiles.

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Figure S13. (a) P3-based PTFT performances measured in the air and under vacuum

(10−4 mbar) after 1 week storage under ambient laboratory air conditions; (b)

Time-dependent performance changes for P3- and P4-based PTFTs stored under

ambient laboratory air conditions and measured in a vacuum chamber (10−4 mbar); (c

and d) The corresponding transfer curves; (e) The operation stability of P3-based

PTFTs with 100 cycles of the hysteresis test at VGS = 60 V; (f) Bias stress stability of

P3-based PTFTs with a continuous bias voltage of 60 V for up to 1000 s.

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(6) Materials

All chemicals were purchased from Tokyo Chemical Industry (TCI), Kanto Chemical

Co., Inc., Wako Pure Chemical Industries, and Sigma Aldrich, and used as received

unless otherwise stated. All reactions were carried out under a N2 atmosphere.

Synthesis of 4-bromo-7-(4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (1)S2

Under N2 atmosphere, a mixture of 4,7-dibromo-benzothiadiaozle (0.65 g, 2.2 mmol),

3-hexyl-5-tributylstannylthiophene (1.1 g, 2.4 mmol), Pd(PPh3)4 (0.15 g, 0.13 mmol),

and anhydrous THF (30 mL) were added to a 50 mL dried two-neck round-bottom

flask. Then, the mixture was stirred at 75 °C for 24 h. After cooling to room

temperature, the mixture was extracted with dichloromethane, dried with anhydrous

Na2SO4, filtered and concentrated under reduced pressure. The crude product was

further purified by silica gel column chromatography (eluent:

hexane/dichloromethane, v/v = 10:1), affording a yellow solid (0.30 g, 36%).

1H NMR (CDCl3, 300 MHz): δ= 7.98 (s, 1H), 7.87 (d, J = 6.0 Hz, 1H), 7.69 (d, J =

6.0 Hz, 1H), 7.09 (s, 1H), 2.72 (t, J = 9.0 Hz, 2H), 1.75 (m, 2H), 1.46 (m, 2H), 1.32

(m, 4H), 0.91 (t, J = 9.0 Hz, 3H) ppm.

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Synthesis of (E)-1,2-bis(7-(4-hexylthiophen-2-yl)benzothiadiazol-4-yl)ethene (3)

Under N2 atmosphere, a mixture of

4-bromo-7-(4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (0.58 g, 1.5 mmol),

(E)-1,2-bis(tributylstannyl)ethene (0.44 g, 0.72 mmol), Pd(PPh3)4 (0.16 g, 0.14 mmol),

and toluene (30 mL) were added to a 50 mL dried two-neck round-bottom flask. Then,

the mixture was stirred at 115 °C for 24 h. After cooling to room temperature, the

mixture was extracted with dichloromethane, dried with anhydrous Na2SO4, filtered

and concentrated under reduced pressure. The crude product was further purified by

silica gel column chromatography (eluent: hexane/dichloromethane, v/v = 1:1),

affording a red solid (0.33 g, 73%).

1H NMR (300 MHz, CDCl3): δ = 8.24 (s, 2H), 7.90 (s, 2H), 7.70 (d, J = 6.0 Hz, 2H),

7.59 (d, J = 6.0 Hz, 2H), 6.98 (s, 2H), 2.67 (t, J = 6.0 Hz, 4H), 1.77-1.63 (m, 4H),

1.46-1.17 (br, 12H), 0.89 (t, J = 6.0 Hz, 6H) ppm; 13C NMR (75 MHz, CDCl3): δ =

154.12, 152.96, 144.63, 139.45, 129.44, 129.32, 128.83, 127.79, 126.97, 125.56,

121.93, 31.86, 30.80, 30.56, 29.23, 22.77, 14.17 ppm; IR (neat): = 2954, 2922, 2853,

1866, 1669, 1612, 1566, 1538, 1523, 1492, 1456, 1395, 1376, 1261, 1190, 1142, 1093,

1022, 970, 936, 903, 868, 813, 795, 774, 723, 692, 648, 615 cm−1; MALDI-TOF MS

(Mw = 628.9): found m/z = 628.7 [M+].

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Synthesis of

(E)-1,2-bis(7-(4-hexyl-5-(trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazol

-4-yl)ethene (BBTV)

At –78 °C, LDA (1.5 M in THF, 1.44 mmol, 1.44 mL) was dropwise added to a

solution of (E)-1,2-bis(7-(4-hexylthiophen-2-yl)benzothiadiazol-4-yl)ethene (0.30 g,

0.48 mmol) in dry THF (50 mL) under N2. The deep purple solution was then stirred

at –30 oC for 60 min. This was followed by the addition of a solution of trimethyltin

chloride in THF (1 M, 1.92 mL, 1.92 mmol). The reaction mixture was then allowed

to slowly warm to room temperature and stirred overnight. Water was added to

quench the reaction. Diethyl ether was added, and the mixture was washed with brine

(100 mL 3). The solution was then dried with anhydrous Na2SO4. The solvents were

removed, and the title compound was purified by recrystallization from

THF/methanol three times and further purified by using a recycling HPLC (0.25 g,

55%).


7.73 (d, J = 6.0 Hz, 2H), 2.71 (t, J = 7.2 Hz, 4H), 1.71-1.64 (m, 4H), 1.42-1.34 (m,

12H), 0.93-0.89 (t, J = 6.0 Hz, 6H), 0.54 (t, J = 30 Hz, 18H, for -SnMe3) ppm; 13C

NMR (75 MHz, CDCl3): δ = 154.72, 153.54, 152.85, 145.41, 135.68, 131.01, 129.76,

129.45, 128.52, 127.44, 126.23, 33.62, 32.72, 32.38, 29.95, 23.19, 14.59, −7.27 ppm;

IR (neat):= 2954, 2925, 2854, 2359, 1716, 1565, 1523, 1489, 1458, 1378, 1269,

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1190, 992, 966, 903, 845, 825, 769, 714, 675, 649, 622 cm−1; MALDI-TOF MS (Mw

= 954.6): found m/z = 954.7 [M+].

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Synthesis of 4-bromo-5-fluoro-7-(4-hexylthiophen-2-yl)benzothiadiazole (2)

Under N2 atmosphere, a mixture of 4,7-dibromo-5-fluorobenzothiadiazole (0.69 g, 2.2

mmol), 3-hexyl-5-tributylstannylthiophene (1.1 g, 2.4 mmol), Pd(PPh3)4 (0.15 g, 0.13

mmol), and toluene (30 mL) were added to a 50 mL dried two-neck round-bottom

flask. Then, the mixture was stirred at 115 °C for 24 h. After cooling to room

temperature, the mixture was extracted with dichloromethane, dried with anhydrous

Na2SO4, filtered and concentrated under reduced pressure. The crude product was

further purified by silica gel column chromatography (eluent:

hexane/dichloromethane, v/v = 2:1), affording a yellow solid (0.63 g, 72%).

1H NMR (CDCl3, 300 MHz): δ = 7.95 (s, 1H), 7.65 (d, J = 6.0 Hz, 1H), 7.10 (s, 1H),

2.69 (t, J = 6.0 Hz, 2H), 1.70-1.64 (m, 2H), 1.41-1.32 (m, 6H), 0.91 (t, J = 6.0 Hz, 3H)

ppm; 13C NMR (CDCl3, 75 MHz): δ = 162.95, 159.61, 154.83, 149.44, 145.26,

137.39, 131.03, 128.13, 123.66, 116.05, 32.18, 31.02, 30.88, 29.52, 23.12, 14.58 ppm;

IR (neat):= 3102, 2961, 2925, 2874, 2850, 2363, 1587, 1487, 1457, 1438,

1431,1421, 1386, 1373, 1359, 1333, 1322, 1311, 1298, 1192, 1156,1112, 1049, 928,

908, 850, 838, 757, 734, 697, 634 cm−1; MALDI-TOF MS (Mw = 399.3): m/z = 399.5

[M+].

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Synthesis of

(E)-1,2-bis(5-fluoro-7-(4-hexylthiophen-2-yl)benzothiadiazol-4-yl)ethene (4)

Under N2 atmosphere, a mixture of

7-bromo-5-fluoro-4-(4-hexylthiophen-2-yl)benzothiadiazole (0.40 g, 1.0 mmol),

(E)-1,2-bis(tributylstannyl)ethene (0.30 g, 0.50 mmol), Pd(PPh3)4 (0.16 g, 0.14 mmol),

and toluene (30 mL) were added to a 50 mL dried two-neck round-bottom flask. Then,

the mixture was stirred at 115 °C for 24 h. After cooling to room temperature, the

mixture was extracted with dichloromethane, dried with anhydrous Na2SO4, filtered

and concentrated under reduced pressure. The crude product was further purified by

silica gel column chromatography (eluent: from hexane/CHCl3 (v/v = 1:1) to CHCl3)

and further recrystallization from CHCl3/methanol mixtures, affording a red solid

(0.23 g, 70%).

1H NMR (300 MHz, 1,1,2,2-Tetrachloroethane-d2, C2D2Cl4, 120 oC): δ = 8.79 (s, 2H),

8.00 (s, 2H), 7.76 (d, J = 12 Hz, 2H), 7.15 (s, 2H), 2.67 (t, J = 7.2 Hz, 4H), 1.70-1.59

(m, 4H), 1.36-1.26 (m, 12H), 1.00-0.92 (m, 6H) ppm; 13C NMR (75 MHz,

1,1,2,2-Tetrachloroethane-d2, C2D2Cl4, 120 oC): δ = 159.86, 154.40, 150.34, 144.85,

138.32, 130.64, 124.49, 123.29, 116.35, 116.16, 114.51, 31.63, 30.66, 30.35, 29.02,

22.54, 13.88 ppm; IR (neat): = 2962, 2922, 2853, 2362, 2341, 2231, 1096, 1054,

1005, 949, 895, 885, 853, 829, 801, 777, 765, 702, 659, 650, 628 cm−1; MALDI-TOF

MS (Mw = 664.9): m/z = 665.2 [M+].

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Synthesis of

(E)-1,2-bis(5-fluoro-7-(4-hexyl-5-(trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]t

hiadiazol-4-yl)ethene (BBTV-F)

At –30 ° C, LDA (1.5 M in THF, 1.44 mmol, 1.44 mL) was dropwise added to a

solution of (E)-1,2-bis(5-fluoro-7-(4-hexylthiophen-2-yl)benzothiadiazol-4-yl)ethene

(0.30 g, 0.48 mmol) in dry THF (50 mL) under N2. The deep purple solution was then

stirred at –30 °C for 60 min. This was followed by the addition of a solution of

trimethyltin chloride in THF (1 M, 1.92 mL, 1.92 mmol). The reaction mixture was

then allowed to slowly warm to room temperature and stirred overnight. Water was

added to quench the reaction. Diethyl ether was added, and the mixture was washed

with brine (100 mL 3). The solution was then dried with anhydrous Na2SO4. The

solvents were removed, and the title compound was purified by recrystallization from

THF/methanol three times and further purified by using a recycling HPLC (0.21 g,

45%).


2.69 (t, J = 9.0 Hz, 4H), 1.70-1.63 (m, 4H), 1.51-1.35 (m, 12H), 1.00-0.92 (t, J = 6.0

Hz, 6H), 0.54 (t, J = 30 Hz, 18H, for Sn(Me)3) ppm; 13C NMR (75 MHz, CDCl3): δ =

159.56, 154.27, 152.32, 150.27, 143.50, 136.75, 131.12, 127.02, 124.05, 116.31,

114.45, 32.92, 32.04, 31.75, 29.31, 22.57, 13.93, −7.90 ppm; IR (neat):= 2962,

2922, 2853, 2362, 2341, 2231, 1096, 1054, 1005, 949, 895, 885, 853, 829, 801, 777,

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765, 702, 659, 650, 628cm−1; MALDI-TOF MS (Mw = 990.6): found m/z = 990.7

[M+].

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Synthesis of

(E)-1,2-bis(7-(5-bromo-4-hexylthiophen-2-yl)-5-fluorobenzothiadiazol-4-yl)ethene

Under N2 atmosphere,

(E)-1,2-bis(5-fluoro-7-(4-hexylthiophen-2-yl)benzothiadiazol-4-yl)ethene (0.070 g,

0.11 mmol) and THF/DMF (20/20 mL) were added to a 100 mL two-neck

round-bottom flask. NBS (2.5 eq, 0.28 g, 1.6 mmol) was added to the flask under N2

flow. The reaction mixture was then stirred at 40 oC for 5 h. After cooling down to

room temperature, the reaction mixture was concentrated in vacuo. After

reprecipitation into methanol (50 mL), the title compound was obtained by

recrystallization from CHCl3/methanol mixtures (0.08 g, 85%).

1H NMR (300 MHz, 1,1,2,2-Tetrachloroethane-d2, C2D2Cl4, 120 oC): δ = 8.71 (s, 2H),

7.81 (s, 2H), 7.67 (d, J = 6.0 Hz, 2H), 2.74 (t, J = 6.0 Hz, 4H), 1.80-1.76 (m, 4H),

1.60-1.37 (m, 12H), 1.09-0.91 (m, 6H) ppm; 13C NMR (75 MHz,

1,1,2,2-Tetrachloroethane-d2, C2D2Cl4, 120 oC): δ = 161.86, 159.27, 154.26, 151.10,

150.00, 143.48, 137.76, 129.14, 124.64, 115.64, 113.23, 31.54, 29.74, 29.50, 28.92,

22.44, 13.78 ppm; IR (neat):= 3090, 2954, 2924, 2854, 1489, 1426, 1376, 1289,

985, 889, 851, 768, 703, 661, 653 cm−1; MALDI-TOF MS (Mw = 822.7): m/z = 823.1

[M+].

S32

Synthesis of

2,7-bis(2-decyltetradecyl)-4,9-bis((E)-2-(tributylstannyl)vinyl)benzo[lmn][3,8]phe

nanthroline-1,3,6,8(2H,7H)-tetraone (NDIV)

NDI (0.20 g, 0.18 mmol), (E)-1,2-bis(tributylstannyl)ethene (0.65 g, 1.1 mmol),

Pd(PPh3)4 (0.020 g, 0.017 mmol), and dry toluene (50 mL) were added to a two

necked round bottom flask. After the mixture was de-gassed for 10 min, it was stirred

at 90 °C for 12 h. After cooling down to room temperature, the solvent was removed

and the crude product was purified by silica gel column chromatography (eluent: from

hexane/CH2Cl2 v/v = 10:1 to v/v = 3:1), affording yellow oil (0.23 g, 40%).

1H NMR (300 MHz, CDCl3): δ = 8.93 (s, 2H), 8.37 (d, J = 21.0 Hz, 2H), 7.33 (d, J =

21.0 Hz, 2H), 4.13 (d, J = 6.0 Hz, 4H), 2.00 (br, 2H), 1.68 (m, 12H), 1.50-1.30 (m,

92H), 1.13 (m, 12H), 1.07 (t, J = 9.0 Hz, 18H), 0.88 (t, J = 9.0 Hz, 12H) ppm; 13C

NMR (75 MHz, CDCl3): δ = 164.33, 163.86, 145.05, 144.18, 142.66, 132.72, 127.28,

126.09, 120.33, 45.14, 37.01, 32.33, 32.19, 30.45, 30.09, 30.06, 30.05, 29.76, 29.74,

29.54, 27.81, 26.88, 23.04, 14.45, 14.00, 10.29 ppm; IR (neat): = 2955, 2922, 2853,

1700, 1661, 1577, 1462, 1442, 1376, 1304, 1262, 1206, 1182, 984, 771, 718, 687, 662,

634 cm−1; MALDI-TOF MS (Mw = 1569.7): found m/z = 1569.9 [M+].

S34

Synthesis of copolymers

General synthetic procedure of copolymers under Pd(0)/CuI co-catalyzed Stille

polycondensation conditions according to the literatureS1:

A mixture of ditin-compound (BBTV, BBTV-F, or NDIV, 0.15 mmol),

dibromo-compound (NDI, BBTV-F-Br, or SNT, 0.15 mmol), Pd2(dba)3 (0.005 g,

0.005 mmol), P(o-tolyl)3 (0.006 g, 0.02 mmol), and CuI (0.004 g, 0.02 mmol) in

chlorobenzene (3 mL) was refluxed for 48 h under N2. After cooling down to room

temperature, the reaction mixture was poured into methanol (200 mL). Hydrochloric

acid (1N, 10 mL) was added to the methanol solution. After stirring for 20 min, the

precipitate was collected by filtration and purified with Soxhlet extraction using

methanol, acetone, hexane, and chloroform. The chloroform soluble fraction was

concentrated and reprecipitated into methanol, yielding the product.

S35

P1 Yield: 80%. GPC (o-dichlorobenzene, at 40 oC): Mn =18.2 kg mol−1, PDI = 1.5; 1H

NMR (300 MHz, CDCl3): δ = 8.84-8.79 (br), 8.64-8.55 (br), 8.20-8.10 (br), 8.00-7.87

(br), 4.22-4.10 (br), 3.14-3.10 (br), 2.75-2.50 (br), 2.00-1.95 (br), 1.75-1.55 (br),

1.49-1.00 (br), 0.95-0.75 (br) ppm; IR (neat):= 2958, 2921, 2851, 1705, 1666, 1577,

1494, 1463, 1435, 1421, 1306, 1260, 1221, 1195, 1089, 1020, 795, 768, 723 cm−1.

S36



(br), 7.82-7.80 (br), 4.09-4.05 (br), 3.15-3.13 (br), 2.48-2.25 (d, 2H), 1.96-1.90 (br),

1.75-1.50 (br), 1.45-1.02 (br), 0.97-0.78 (br) ppm; IR (neat):= 2958, 2922, 2852,

1704, 1667, 1578, 1542, 1464, 1437, 1307, 1261, 1093, 1022, 854, 801 cm−1.

S37



(br), 6.90-6.80 (br), 6.79-6.70 (br), 4.27-4.20 (br), 2.80-2.75 (br), 1.85-1.10 (br),

0.90-0.75 (br) ppm; IR (neat):= 2957, 2922, 2852, 1697, 1652, 1583, 1508, 1458,

1443, 1318, 1259, 1195, 1091, 1019, 799 cm−1.

S38


NMR (300 MHz, CDCl3): δ = 8.82-8.75 (br), 7.79-7.70 (br), 7.54-7.45 (br), 6.91- 6.89

(br), 6.81-6.78 (br), 4.26-4.20 (br), 2.81-2.78 (br), 2.31-2.20 (br), 1.54-1.10 (br),

0.93-0.78 (br) ppm; IR (neat):= 3078, 2952, 2920, 2851, 1697, 1652, 1571, 1508,

1458, 1442, 1375, 1318, 1256, 1219, 1191, 1105, 1027, 951, 930, 797, 772, 732, 657

cm−1.

S39

References

(S1) Wang, Y.; Hasegawa, T.; Matsumoto, H.; Mori, T.; Michinobu, T. Significant

Improvement of Unipolar n-Type Transistor Performances by Manipulating the

Coplanar Backbone Conformation of Electron-Deficient Polymers via

Hydrogen-Bonding. Adv. Mater. 2018, 30, 1707164.

(S2) Zhang, J.; Yang, Y.; He, C.; He, Y.; Zhao, G.; Li, Y. Solution-Processable

Star-Shaped Photovoltaic Organic Molecule with Triphenylamine Core and

BenzothiadiazoleThiophene Arms. Macromolecules 2009, 42, 7619−7622.

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