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(frit S3) and dried to a constant weight. Yield: 0.3581 g
(81%). SEC (THF): Mw 5 6800, Mn 5 3300, Ð 5 2.06, P 5 10–
11 (Fig. 1). FI IR (ATR): m 5 2922, 2850, 2228, 1607, 1460,
1350, 1270, 1167, 1009, 808, 740, 558 cm21 (Supporting
1
Information Fig. S18). H-NMR (300.13 MHz, CDCl3, d): 7.95–
7.10 (m, 10H, aromatic H), 6.88–6.78 (m, 1H, heterocyclic
H), 2.15–1.45 (br d, 4H, 2 3 fluorene–CH2), 1.25–0.95 (m,
20 H, 10 3 CH2), 0.81 (t, 6H, 2 3 CH3), 0.70–0.45 (br s
shoulder, 4H, 2 3 CH2–Me) (Supporting Information Fig.
S19). 13C-NMR (75.45 MHz, CDCl3, d): 153.4, 152.0, 151.8,
151.6, 151.2, 146.1, 142.4, 141.5, 140.5, 139.9, 138.1, 132.7,
132.4, 129.8, 128.8, 128.5, 128.1, 125.0, 124.0, 120.1 (20C
aromatic), 118.6 (CꢀN), 115.6, 111.2, 111.0, 110.2 (4C aro-
matic), 55.2 (5C(octyl)2), 40.4 (2C), 31.8 (2C), 30.0 (2C),
29.8 (2C), 29.3 (2C), 23.8 (2C), 22.7 (2C), 14.1 (2C), all ali-
phatic (Supporting Information Fig. S20).
FIGURE 1 SEC curves of the PFTT–PhCN (dashed), OFDTT–
PhCN (dashed and dotted), and PFDTT–PhCN (solid) copoly-
mers measured in THF as the mobile phase (polystyrene stand-
ards were used for calibration).
Poly/Oligo{9,9-dioctylfluorene-2,7-diyl-alt-3,5-bis(40-
cyanophenyl)dithieno[3,2-b:20,30-d]thiophene-2,6-diyl}
(PFDTT–PhCN or OFDTT–PhCN)
(a) OFDTT–PhCN: High Temperature (130 8C) Procedure in
Xylene/NaHCO3
Packard 34401A multimeter. All measurements were con-
ducted in a glove box under a nitrogen atmosphere.
Comonomers F (0.3909 g, 0.7 mmol) and Br–DTT–PhCN (10)
(0.3894 g, 0.7 mmol) were weighted into a dry preheated
three-necked reactor equipped with a condenser, magnetic stir-
rer, argon inlet, and septum and the reaction vessel was
flushed with argon (30 min). Then degassed xylene (10 mL),
degassed aqueous (15 wt. %) NaHCO3 (10 mL), and Aliquat
336 (40 mg) were added by a syringe via septum and the mix-
ture was flushed with argon for 30 min at 50 8C. The tempera-
ture was increased to 130 8C and the catalyst Pd(PPh3)4
(48 mg, 3.0 mol % per total monomer) in degassed xylene
(5 mL) was added via septum. Reaction mixture was heated at
130 8C for 120 min under argon. Then end-capping was per-
formed: (a) with phenylboronic acid pinacol ester (0.05 g, 0.25
mmol, 15 min, 130 8C) and (b) with 2-ethylhexyl bromide
(0.2 mL, 1.12 mmol, 15 min, 130 8C). After cooling, the reac-
tion mixture was separated into water layer (aq. NaHCO3, bot-
tom, wasted), organic layer (xylene, upper), and insoluble
material (on the walls and magnetic stirrer bar). The insoluble
material was dissolved in THF, mixed with xylene layer, and
precipitated into an excess of methanol. The precipitate was
filtered off (S3), washed with water and methanol, and dried.
Yield: 0.2698 g (49%). The raw material was dissolved in THF,
Synthesis
Organic Synthesis
Organic syntheses of new monomers, 4-(2,5-dibromo-
thieno[3,2-b]thiophen-3-yl)benzonitrile (Br–TT–PhCN) and
4,40-(2,6-dibromodithieno-[3,2-b:20,30-d]thiophene-3,5-diyl)di-
benzonitrile (Br–DTT–PhCN), and their characterization are
described in Supporting Information.
Polymer Synthesis
Poly{9,9-dioctylfluorene-2,7-diyl-alt-3-(40-cyanophenyl)
thieno[3,2-b]thiophene-2,5-diyl} (PFTT–PhCN)
Comonomers F (0.3909 g, 0.7 mmol) and Br–TT–PhCN (5)
(0.2794 g, 0.7 mmol) were weighted into a dry preheated
three-necked reactor equipped with a condenser, magnetic
stirrer, argon inlet and septum and the reaction vessel was
flushed with argon (30 min). Then degassed xylene (10 mL),
degassed aqueous (15 wt. %) NaHCO3 (10 mL), and Aliquat
336 (40 mg) were added by a syringe via septum and the
mixture was flushed with argon for 30 min at 50 8C. The
temperature was increased to 130 8C and the catalyst
Pd(PPh3)4 (32.3 mg, 2.0 mol % per total monomer) in
degassed xylene (5 mL) was added via septum. Reaction
mixture was heated at 130 8C for 90 min under argon. Then
end-capping was performed: (a) with phenylboronic acid
pinacol ester (0.05 g, 0.25 mmol, 15 min, 130 8C) and (b)
with 2-ethylhexyl bromide (0.2 mL, 1.12 mmol, 15 min, 130
8C). After cooling, the upper organic layer of reaction mixture
was poured into an excess of methanol and the precipitated
raw material was filtered off (frit S3), washed with water
and methanol, and dried. Yield: 0.3905 g (89%). The raw
polymer was dissolved in THF, filtered through a short col-
R
filtered through a short column of CeliteV 577/aluminum
oxide/silica gel 60 (ca. 1 4 3 3/3/3 cm), and the volume
was reduced to ca. 15–20 mL by a rotary evaporator. The solu-
tion was precipitated into methanol (700 mL), the khaki-green
oligomer OFDTT–PhCN was filtered off (S3) and dried to a
constant weight. Yield: 0.2387
g
(43%). SEC (THF):
Mw 5 1550, Mn 5 1300, Ð 5 1.19, P 5 2–3 (Fig. 1). FI IR (ATR):
m 5 2922, 2850, 2324, 2228, 1605, 1524, 1460, 1340, 1270,
1170, 1020, 840, 812, 740, 550 cm21 (Supporting Information
1
Fig. S21). H-NMR (300.13 MHz, CDCl3, d): 8.05–6.60 (m, aro-
R
umn of CeliteV 577/aluminum oxide/silica gel 60 (ca. 1 4
3 3/3/3 cm) and the volume was reduced to ca. 15 mL by a
rotary evaporator. The solution was precipitated into metha-
nol (700 mL), the ochre polymer PFTT–PhCN was filtered off
matic H), 2.35–1.45 (m, fluorene–CH2), 1.45–0.90 (m, CH2),
0.81 (s, CH3), 0.54 (br s, CH2–Me) (ratio aliphatic to aromatic
protons is 3.46) (Supporting Information Fig. S22). 13C-NMR
(75.45 MHz, CDCl3, d): 156.1, 153.4, 151.7, 150.8, 141.7, 141.4,
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