Supporting Information for:
Synthesis of polyisocyanides bearing oligothiophene pendants:
Higher-order structural control through pendant framework design
Tomoyuki Ikai1, Yugaku Takagi1, Ken-ichi Shinohara2, Katsuhiro Maeda1 and
Shigeyoshi Kanoh1
1Graduate
School of Natural Science and Technology,
Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan;
2School
of Materials Science, Japan Advanced Institute of Science and
Technology (JAIST), 1-1 Asahi-dai, Nomi 923-1292, Japan.
*Correspondence: Professor Tomoyuki Ikai,
Graduate School of Natural Science and Technology,
Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
E-mail: ikai@se.kanazawa-u.ac.jp
Tel.: +81 76 234 4781; Fax: +81 76 234 4781
1
Materials
The anhydrous solvents (toluene, N,N-dimethylformamide (DMF) and tetrahydrofuran
(THF)), the common organic solvents and potassium carbonate (K2CO3) were
purchased
from
Kanto
(Tokyo,
Japan).
Hydrazine
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene
monohydrate,
and
2-(2-aminoethyl)thiophene (1c-1) were bought from Tokyo Kasei (TCI, Tokyo, Japan).
N-Bromosuccinimide (NBS), phthalic anhydride and n-butyllithium (1.6 M in
n-hexane) were purchased from Wako (Osaka, Japan). Tributyltin chloride was from
Aldrich (Milwaukee, WI, USA). Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4)
was purchased from Nacalai (Kyoto, Japan). 2-Hexyl-5-tributylstannylthiophene (1a-1)1,
2-bromo-5-(2-octyldodecyl)thiophene (1b-1)2 and 2-bromo-3-hexylthiophene3 were
prepared according to the procedures in the literature.
2
Synthesis
Oligothiophene units 1a–1c were prepared according to Scheme S1.
Scheme S1 Synthesis of oligothiophene units (1a–1c).
Synthesis
of
1a-2.
To
a
solution
of
1a-1
(26.7
g,
58.3
mmol)
and
2-bromo-3-hexylthiophene (11.1 g, 44.8 mmol) in toluene/DMF (4/1, v/v, 200 mL) was
added Pd(PPh3)4 (1.55 g, 1.34 mmol) under a nitrogen atmosphere. After stirring at
120 °C for 3 h under microwave heating, the reaction mixture was diluted with hexane,
washed with water, and then dried over Na2SO4. The obtained solution was passed
through a short pad of silica gel using hexane as the eluent to remove the metal catalyst.
After evaporating the solvent, compound 1a-2 (15.3 g) was obtained as a pale yellow oil
and was used for the next step without further purification. 1H NMR (500 MHz, CDCl3,
rt):  7.12 (d, J = 5.2 Hz, 1H), 6.92-6.89 (m, 2H), 6.71 (d, J = 4.0 Hz, 1H), 2.80 (t, J =
7.4 Hz, 2H), 2.72 (t, J = 7.7 Hz, 2H), 1.73-1.57 (m, 4H), 1.45-1.20 (m, 12H), 0.93-0.83
3
(m, 6H).
Synthesis of 1a-3. To a solution of 1a-2 (7.00 g, 20.9 mmol) in DMF (21 mL) was
added NBS (3.54 g, 19.9 mmol) at 0 °C. After stirring at 0 °C for 3 h, the reaction
mixture was diluted with hexane, washed with saturated NaHCO3 aqueous solution and
water, and then dried over Na2SO4. After removing the solvent by evaporation, the
crude product was purified by silica gel chromatography using hexane as the eluent to
give the desired product as a pale yellow oil (7.66 g, 89% yield). 1H NMR (500 MHz,
CDCl3, rt) :  6.86 (s, 1H), 6.85 (d, J = 2.9 Hz, 1H), 6.70 (d, J = 2.9 Hz, 1H), 2.79 (t, J =
7.7 Hz, 2H), 2.65 (t, J = 7.7 Hz, 2H), 1.76-1.51 (m, 4H), 1.49-1.22 (m, 12H), 0.98-0.82
(m, 6H).
Synthesis
of
1a-4.
To
a
solution
of
1a-3
(7.66
g,
18.5
mmol)
and
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene (7.58 g, 25.8 mmol) in
toluene/2 M K2CO3 aqueous solution (2/1, v/v, 160 mL) was added Pd(PPh3)4 (639 mg,
0.55 mmol) under a nitrogen atmosphere. After stirring at 90 °C for 4 h under
microwave heating, the reaction mixture was diluted with hexane, washed with water,
and then dried over Na2SO4. After removing the solvent by evaporation, the crude
product was purified by silica gel chromatography using hexane as the eluent to give the
desired product as an orange oil (7.75 g, 84% yield). 1H NMR (500 MHz, CDCl3, rt): 
7.20 (dd, J = 5.2, 1.0 Hz, 1H), 7.16 (dd, J = 5.2, 1.0 Hz , 1H), 7.08-7.00 (m, 3H), 6.98 (s,
1H), 6.92 (d, J = 3.4 Hz, 1H), 6.72 (d, J = 3.4 Hz, 1H), 2.80 (t, J = 7.6 Hz, 2H), 2.71 (t,
J = 7.9 Hz, 2H), 1.75-1.59 (m, 4H), 1.46-1.24 (m, 12H), 0.96-0.84 (m, 6H).
Synthesis of 1a-5. To a solution of 1a-4 (7.75 g, 15.5 mmol) in anhydrous THF (56 mL)
was added dropwise n-butyllithium (1.6 M in hexane, 10.8 mL, 17.3 mmol) via syringe
at -78 °C under nitrogen atmosphere. After stirring at -78 °C for 2 h, tributyltin chloride
(6.43 mL, 21.5 mmol) was added. The mixture was warmed to room temperature and
stirred for 2 h. After quenching the reaction with water, the volatile species were
4
evaporated in vacuo. The residue was extracted with hexane, and the organic layer was
washed with water, dried over anhydrous Na2SO4, and concentrated. Compound 1a-5
(14.5 g) was obtained as a pale yellow oil and was used for the next step without further
purification. 1H NMR (500 MHz, CDCl3, rt):  7.28 (d, J = 3.4 Hz, 1H), 7.06 (t, J = 3.4
Hz, 2H), 7.02 (d, J = 3.8 Hz, 1H), 6.97 (s, 1H), 6.92 (d, J = 3.4 Hz, 1H), 6.74 (d, J = 3.4
Hz, 1H), 2.80 (t, J = 7.6 Hz, 2H), 2.71 (t, J = 7.9 Hz, 2H), 1.73-1.51 (m, 10H),
1.43-1.27 (m, 18H), 1.14-1.10 (m, 6H), 0.96-0.85 (m, 15H).
Synthesis of 1a-6. To a solution of 1a-5 (1.76 g) and 1c-2 (3.77 g, 4.78 mmol) in
toluene/DMF (4/1, v/v, 24 mL) was added Pd(PPh3)4 (165 mg, 0.14 mmol) under a
nitrogen atmosphere. After stirring at 120 °C for 3 h under microwave heating, the
reaction mixture was diluted with hexane/ethyl acetate (1/1, v/v), washed with water,
and then dried over Na2SO4. After removing the solvent by evaporation, the crude
product was purified by silica gel chromatography using hexane/CH2Cl2 (1/1, v/v) as
the eluent to give the desired product as an orange solid (3.60 g, 99% yield). 1H NMR
(500 MHz, CDCl3, rt):  7.85 (dd, J = 5.6, 3.0 Hz, 2H), 7.72 (dd, J = 5.2, 2.9 Hz, 2H),
7.05-7.01 (m, 3H), 7.00-6.95 (m, 3H), 6.93 (d, J = 3.4 Hz, 1H), 6.79 (d, J = 3.4 Hz, 1H),
6.73 (d, J = 3.4 Hz, 1H), 3.98 (t, J = 7.4 Hz, 2H), 3.20 (t, J = 7.4 Hz, 2H), 2.81 (t, J =
7.7 Hz, 2H), 2.71 (t, J = 8.0 Hz, 2H), 1.73-1.61 (m, 4H), 1.44-1.27 (m, 12H), 0.94-0.85
(m, 6H).
Synthesis of 1a. To a solution of 1a-5 (3.07 g, 4.07 mmol) in THF (41 mL) was added
hydrazine monohydrate (1.78 mL, 36.6 mmol) under a nitrogen atmosphere. After
stirring at 75 °C for 12 h, the reaction mixture was filtered to remove the solid
byproduct. The filtrate was diluted with CH2Cl2, washed with water, and then dried over
Na2SO4, and concentrated. Compound 1a (2.53 g) was obtained as a pale yellow oil and
was used for the next step without further purification. 1H NMR (500 MHz, CDCl3, rt):
 7.07-7.02 (m, 3H), 7.01 (d, J = 3.4 Hz, 2H), 6.98 (s, 1H), 6.93 (d, J = 3.4 Hz, 1H),
6.75 (d, J = 3.4 Hz, 1H), 6.73 (d, J = 3.4 Hz, 1H), 3.00 (brt, 2H), 2.93 (t, J = 6.3 Hz,
5
2H), 2.81 (t, J = 7.7 Hz, 2H), 2.71 (t, J = 8.0 Hz, 2H), 1.74-1.57 (m, 4H), 1.45-1.27 (m,
12H), 1.21-1.07 (brs, 2H), 0.95-0.85 (m, 6H).
Synthesis of 1b-2. To a solution of 1b-1 (4.00 g, 9.02 mmol) in anhydrous THF (32 mL)
was added dropwise n-butyllithium (1.6 M in hexane, 5.91 mL, 9.45 mmol) via syringe
at -78 °C under nitrogen atmosphere. After stirring at -78 °C for 2 h, tributyltin chloride
(3.24 mL, 10.8 mmol) was added. The mixture was warmed to room temperature and
stirred for 2 h. After quenching the reaction with water, the volatile species were
evaporated in vacuo. The residue was extracted with hexane, and the organic layer was
washed with water, dried over anhydrous Na2SO4, and concentrated. Compound 1b-2
(7.16 g) was obtained as a pale yellow oil and was used for the next step without further
purification. 1H NMR (500 MHz, CDCl3, rt):  6.97 (d, J = 3.1 Hz, 1H), 6.86 (d, J = 3.1
Hz, 1H), 2.79 (d, J = 6.9 Hz, 2H), 1.90-1.80 (m, 1H), 1.80-1.50 (m, 8H), 1.42-1.20 (m,
36H), 1.16-1.04 (m, 6H), 0.96-0.83 (m, 15H).
Synthesis of 1b-3. To a solution of 1b-2 (1.86 g) and 2-bromo-3-hexylthiophene (5.40 g,
8.62 mmol) in toluene/DMF (4/1, v/v, 38 mL) was added Pd(PPh3)4 (260 mg, 0.23
mmol) under a nitrogen atmosphere. After stirring at 120 °C for 3 h under microwave
heating, the reaction mixture was diluted with hexane/ethyl acetate (1/1, v/v), washed
with water, and then dried over Na2SO4. After removing the solvent by evaporation, the
crude product was purified by silica gel chromatography using hexane as the eluent to
give the desired product as a pale yellow oil (2.80 g, 61% yield). 1H NMR (500 MHz,
CDCl3, rt):  7.11 (d, J = 5.2 Hz, 1H), 6.92-6.87 (m, 2H), 6.68 (d, J = 3.4 Hz, 1H),
2.78-2.68 (m, 4H), 1.69-1.56 (m, 3H), 1.44-1.10 (m, 38H), 0.93-0.81 (m, 9H).
Synthesis of 1b-4. To a solution of 1b-3 (2.80 g, 5.27 mmol) in THF/DMF (1/1, v/v, 11
mL) was added NBS (0.89 g, 5.0 mmol) at 0 °C. After stirring at 0 °C for 3 h, the
reaction mixture was diluted with hexane, washed with saturated NaHCO3 aqueous
solution and water, and then dried over Na2SO4. After removing the solvent by
6
evaporation, the crude product was purified by silica gel chromatography using hexane
as the eluent to give the desired product as a pale yellow oil (2.86 g, 89% yield). 1H
NMR (500 MHz, CDCl3, rt):  6.88-6.83 (m, 2H), 6.67 (d, J = 4.0 Hz, 1H), 2.73 (d, J =
6.9 Hz, 2H), 2.66 (t, J = 7.7 Hz, 2H), 1.73-1.55 (m, 3H), 1.51-1.14 (m, 38H), 1.02-0.81
(m, 9H).
Synthesis
of
1b-5.
To
a
solution
of
1b-4
(2.80
g,
4.59
mmol)
and
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene (2.33 g, 7.98 mmol) in
toluene/2 M K2CO3 aqueous solution (2/1, v/v, 41 mL) was added Pd(PPh3)4 (159 mg,
0.14 mmol) under a nitrogen atmosphere. After stirring at 90 °C for 5 h under
microwave heating, the reaction mixture was diluted with hexane, washed with water,
and then dried over Na2SO4. The obtained solution was passed through a short pad of
silica gel using hexane as the eluent to remove the metal catalyst. After evaporating the
solvent, compound 1b-5 (2.88 g) was obtained as an orange oil and was used for the
next step without further purification. 1H NMR (500 MHz, CDCl3, rt):  7.22-7.14 (m,
2H), 7.05 (d, J = 3.4 Hz, 1H), 7.04-6.98 (m, 2H), 6.98 (s, 1H), 6.93 (d, J = 3.4 Hz, 1H),
6.69 (d, J = 3.4 Hz, 1H), 2.79-2.68 (m, 4H), 1.70-1.59 (m, 3H), 1.45-1.18 (m, 38H),
0.96-0.82 (m, 9H).
Synthesis of 1b-6. To a solution of 1b-5 (2.88 g, 4.15 mmol) in anhydrous THF (23 mL)
was added dropwise n-butyllithium (1.6 M in hexane, 4.54 mL, 7.27 mmol) via syringe
at -78 °C under nitrogen atmosphere. After stirring at -78 °C for 2 h, tributyltin chloride
(2.26 mL, 7.53 mmol) was added. The mixture was warmed to room temperature and
stirred for 2 h. After quenching the reaction with water, the volatile species were
evaporated in vacuo. The residue was extracted with hexane, and the organic layer was
washed with water, dried over anhydrous Na2SO4, and concentrated. Compound 1b-6
(6.03 g) was obtained as an orange oil and was used for the next step without further
purification. 1H NMR (500 MHz, CDCl3, rt):  7.30-7.27 (m, 1H), 7.08-7.02 (m, 3H),
6.98 (s, 1H), 6.93 (d, J = 3.2 Hz, 1H), 6.69 (d, J = 3.4 Hz, 1H), 2.77-2.68 (m, 4H),
7
1.72-1.49 (m, 11H), 1.45-1.20 (m, 42H), 1.15-1.08 (m, 6H), 0.96-0.84 (m, 18H).
Synthesis of 1b-7. To a solution of 1b-6 (6.02 g) and 1c-2 (2.91 g, 6.12 mmol) in
toluene/DMF (4/1, v/v, 29 mL) was added Pd(PPh3)4 (200 mg, 0.17 mmol) under a
nitrogen atmosphere. After stirring at 120 °C for 3 h under microwave heating, the
reaction mixture was diluted with hexane/ethyl acetate (1/1, v/v), washed with water,
and then dried over Na2SO4. After removing the solvent by evaporation, the crude
product was purified by silica gel chromatography using hexane/CH2Cl2 (1/1, v/v) as
the eluent to give the desired product as an orange solid (3.05 g, 62% yield). 1H NMR
(500 MHz, CDCl3, rt):  7.85 (dd, J = 5.4, 3.2 Hz, 2H), 7.71 (dd, J = 5.4, 3.2 Hz, 2H),
7.06-7.00 (m, 3H), 7.00-6.95 (m, 3H), 6.93 (d, J = 3.4 Hz, 1H), 6.78 (d, J = 3.4 Hz, 1H),
6.69 (d, J = 3.4 Hz, 1H), 3.98 (t, J = 7.4 Hz, 2H), 3.20 (t, J = 7.4 Hz, 2H), 2.80-2.66 (m,
4H), 1.70-1.60 (m, 3H), 1.47-1.12 (m, 38H), 0.95-0.82 (m, 9H).
Synthesis of 1b. To a solution of 1b-7 (3.00 g, 3.16 mmol) in THF (31 mL) was added
hydrazine monohydrate (1.38 mL, 28.4 mmol) under a nitrogen atmosphere. After
stirring at 75 °C for 14 h, the reaction mixture was filtered to remove the solid
byproduct. The filtrate was diluted with CH2Cl2, washed with water, and then dried over
Na2SO4, and concentrated. Compound 1b (2.65 g) was obtained as a pale yellow oil and
was used for the next step without further purification. 1H NMR (500 MHz, CDCl3, rt):
 7.07-7.03 (m, 3H), 7.03-7.00 (m, 2H), 6.99 (s, 1H), 6.94 (d, J = 3.4 Hz, 1H), 6.76 (d, J
= 2.9 Hz, 1H), 6.70 (d, J = 3.4 Hz, 1H), 3.05-2.98 (m, 2H), 2.94 (t, J = 6.3 Hz, 2H),
2.78-2.69 (m, 4H), 1.73-1.61 (m, 3H), 1.45-1.13 (m, 40H), 0.95-0.85 (m, 9H).
Synthesis of 1c-2. To a solution of 1c-1 (15.8 g, 124 mmol) in DMF (128 mL) was
added phthalic anhydride (20.1 g, 137 mmol). After stirring at 165 °C for 4 h under
microwave heating, NBS (24.4 g, 137 mmol) was added at 0 °C. The reaction mixture
was at 0 °C for 2 h and diluted with CH2Cl2, washed with saturated NaHCO3 aqueous
solution and water, and then dried over Na2SO4. After removing the solvent by
8
evaporation, the crude product was purified by silica gel chromatography using
hexane/CH2Cl2 (1/2, v/v) as the eluent to give the desired product as a white solid (28.9
g, 69% yield). 1H NMR (500 MHz, CDCl3, rt):  7.84 (dd, J = 5.4, 3.2 Hz, 2H), 7.72
(dd, J = 5.4, 3.2 Hz, 2H), 6.84 (d, J = 3.4 Hz, 1H), 6.63 (d, J = 3.4 Hz, 1H), 3.93 (t, J =
7.2 Hz, 2H), 3.15 (t, J = 7.2 Hz, 2H).
Synthesis of 1c-3. To a solution of 1c-2 (3.08 g, 9.17 mmol) and 1a-1 (5.03 g, 11.0
mmol) in toluene/DMF (4/1, v/v, 46 mL) was added Pd(PPh3)4 (0.32 g, 0.28 mmol)
under a nitrogen atmosphere. After stirring at 120 °C for 3 h under microwave heating,
the reaction mixture was diluted with hexane/ethyl acetate (1/1, v/v), washed with water,
and then dried over Na2SO4. After removing the solvent by evaporation, the crude
product was purified by silica gel chromatography using hexane/ethyl acetate (3/1, v/v)
as the eluent to give the desired product as a pale yellow solid (2.66 g, 69% yield). 1H
NMR (500 MHz, CDCl3, rt):  7.85 (dd, J = 5.4, 3.2 Hz, 2H), 7.72 (dd, J = 5.4, 3.2 Hz,
2H), 6.89 (d, J = 4.0 Hz, 2H), 6.75 (d, J = 3.4 Hz, 1H), 6.64 (d, J = 3.4 Hz, 1H), 3.97 (t,
J = 7.4 Hz, 2H), 3.18 (t, J = 7.4 Hz, 2H), 2.76 (t, J = 7.7 Hz, 2H), 1.66 (quint, J = 7.5
Hz, 2H), 1.42-1.23 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H).
Synthesis of 1c. To a solution of 1c-3 (2.66 g, 6.29 mmol) in THF (63 mL) was added
hydrazine monohydrate (2.75 mL, 56.6 mmol) under a nitrogen atmosphere. After
stirring at 75 °C for 4 h, the reaction mixture was filtered to remove the solid byproduct.
The filtrate was diluted with CH2Cl2, washed with water, and then dried over Na2SO4,
and concentrated. Compound c (1.72 g) was obtained as a pale yellow oil and was used
for the next step without further purification. 1H NMR (500 MHz, CDCl3, rt):  6.91 (dd,
J = 6.9, 3.4 Hz, 2H), 6.70 (d, J = 2.9 Hz, 1H), 6.64 (d, J = 3.4 Hz, 1H), 2.98 (t, J = 6.3
Hz, 2H), 2.90 (t, J = 6.6 Hz, 2H), 2.77 (t, J = 7.7 Hz, 2H), 1.71-1.61 (quint, J = 7.5 Hz,
2H), 1.42-1.27 (m, 6H), 1.23 (brs, 2H), 0.88 (t, J = 6.6 Hz, 3H).
9
Supporting data
Figure S1 CD (upper) and absorption (lower) spectra of poly-3a and poly-3b in CHCl3
at 25 °C. The spectra indicated by solid and dotted lines were obtained from polymer
solutions of 3.0 x 10-4 M (cell length: 1.0 mm) and 3.0 x 10-5 M (cell length: 10 mm),
respectively. These concentrations were calculated assuming that there were no
insoluble parts.
10
Figure S2 1H NMR spectra of 3a (a), 3b (b) and 3c (c) in CDCl3 at rt.
11
Figure S3 13C NMR spectra of 3a (a), 3b (b) and 3c (c) in CDCl3 at rt.
12
Figure S4 1H NMR spectra of poly-3a (a), poly-3b (b) and poly-3c (c) in CDCl3 at rt.
13
Captions for supporting movies
Movie S1 Single-molecule imaging of a structural dynamics of poly-3a by a
fast-scanning (high-speed) atomic force microscope (FS-AFM) imaging on mica
substrate under n-octylbenzene at 25 ± 1 ºC. XY: 500 x 375 nm2, Z: 7.2 nm. Rate: 3.0
frames s-1 (play at 15 fps). x-Scan frequency: 3.6 x 102 Hz. Cantilever: USC-F1.2-k0.15
(see Experimental Procedure for detail).
Movie S2 Single-molecule imaging of a structural dynamics of poly-3b by a FS-AFM
on mica substrate under n-octylbenzene at 25 ± 1 ºC. XY: 256 x 192 nm2, Z: 18.0 nm.
Rate: 1.0 frames s-1 (play at 15 fps). x-Scan frequency: 1.8 x 102 Hz. Cantilever:
OMCL-AC10DS (see Experimental Procedure for detail).
14
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15