JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
9-Hexyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)-9H-carbazole (M1)
H), 5.68 (dd, J ¼ 8.5, 2.4 Hz, 1H, Ar-H), 5.50 (dd, J ¼ 8.5, 2.4
Hz, 1H, Ar-H). MS: m/z calcd 710.7; found 711.7. Anal. Calcd
for C28H16F4IrN3O3: C, 47.32; H, 2.27; N, 5.91. Found: C,
47.34; H, 2.04; N, 5.84.
To a solution of 3,6-dibromo-9-hexyl-9H-carbazole (2.51 g,
ꢁ
6.14 mmol) in anhydrous THF (65 mL) at ꢀ78 C was added
n-BuLi (9.8 mL, 24.50 mmol) dropwise. The reaction mixture
was stirred for 2 h at ꢀ78 ꢁC, 2-isopropoxy-4,4,5,5-tetra-
methyl-1,3,2-dioxabrorolane (10 mL, 48.03 mmol) was then
added quickly to the solution. The reaction mixture was
warmed to room temperature and stirred for 24 h. Some
water was poured into the solution and then the organic
layer was extracted with diethyl ether several times. The or-
ganic phase was dried over anhydrous magnesium sulfate.
After evaporation of the solvent, the residue was purified by
column chromatography eluting with ethyl acetate–cyclohex-
ane mixture to give a white solid in 64% yield (1.99 g). 1H
NMR (CDCl3, 500 MHz, ppm): d 8.66 (s, 2H, Ar-H), 7.91 (d, J
¼ 8.2 Hz, 2H, Ar-H), 7.39 (d, J ¼ 7.9 Hz, 2H, Ar-H), 4.32 (t, J
¼ 6.7 Hz, 2H, CH2), 1.86–1.83 (m, 2H, CH2), 1.39 (s, 24H,
CH3), 1.35–1.32 (m, 2H, CH2), 1.30–1.24 (m, 4H, CH2), 0.86
(t, J ¼ 7.0 Hz, 3H, CH3). MS: m/z calcd 503.3; found 504.4.
Elemental Anal. Calcd. for C30H43B2NO4: C, 71.59%; H,
8.61%; N, 2.78%. Found: C, 71.76%; H, 8.40%; N, 2.70%.
3,6-Dibromo-9-(6-bromohexyl)-9H-carbazole (2)
9-(6-Bromohexyl)-9H-carbazole (1.04 g, 3.16 mmol) was dis-
solved in THF (20 mL), to the solution was added n-bromo-
succinimide (1.14 g, 6.32 mmol), then the reaction vessel
was shielded from light by an aluminum foil and stirred for
24 h at 65 ꢁC. The solution was poured into brine and
extracted with dichloromethane then dried over anhydrous
magnesium sulfate. The solution was concentrated and puri-
fied by recrystallization in dichloromethane and methanol as
a white solid in 97% yield (1.49 g). 1H NMR (CDCl3, 500
MHz, ppm): d 8.15 (d, J ¼ 1.8 Hz, 2H, Ar-H), 7.57 (dd, J ¼
8.7, 1.8 Hz, 2H, Ar-H), 7.29 (d, J ¼ 8.7 Hz, 2H, Ar-H), 4.29 (t,
J ¼ 6.9 Hz, 2H, CH2), 3.38 (t, J ¼ 6.9 Hz, 2H, CH2), 1.89–1.75
(m, 4H, CH2), 1.53–1.44 (m, 2H, CH2), 1.44–1.31 (m, 2H,
CH2). Anal. Calcd for C18H18Br3N: C, 44.30; H, 3.72; N, 2.87.
Found: C, 44.54; H, 3.62; N, 2.75.
Monomer M3
Bis(4-bromophenyl)diphenylsilane (M2)
Compounds 1 (76.0 mg, 0.11 mmol), 2 (52.6 mg, 0.11
mmol), potassium carbonate (K2CO3) (16.2 mg, 0.12 mmol)
and 18-crown-6 (1.6 mg, 0.0061 mmol) were dispersed in
10 mL acetonꢁe. The reaction mixture was degassed and then
stirred at 55 C for 48 h. After cooling to room temperature,
the solution was concentrated and the obtained concentra-
tion was purified by column chromatography eluting with ac-
etone–dichloromethane mixture to give a bright yellow solid
1,4-Dibromobenzene (4.72 g, 20 mmol) was dissolved in dry
diethyl ether and cooled to ꢀ78 ꢁC. To the solution was
added n-BuLi (2.5 M, 8.4 mL, 1.05 equiv) dropwise. After
stirred for 2 h, dichlorodiphenylsilane (2.1 mL, 10 mmol)
was added dropwise in one portion. Then the reaction mix-
ture was warmed to room temperature and stirred over-
night. Upon completion, the reaction mixture was poured
into water and extracted with diethyl ether, then the com-
bined organic solution was washed with water and dried
over anhydrous magnesium sulfate. The crude product was
purified by recrystallization in ethanol as a white solid in
1
in 75% yield (90.2 mg). H NMR (DMSO-d6, 500 MHz, ppm):
d 8.58 (d, J ¼ 5.5 Hz, 1H, Ar-H), 8.47 (d, J ¼ 2.0 Hz, 1H, Ar-
H), 8.28 (d, J ¼ 8.5 Hz, 1H, Ar-H), 8.23 (d, J ¼ 8.5 Hz, 1H,
Ar-H), 8.05 (t, J ¼ 8.0 Hz, 1H, Ar-H), 8.00 (t, J ¼ 8.0 Hz, 1H,
Ar-H), 7.76 (d, J ¼ 8.8 Hz, 1H, Ar-H), 7.66 (d, J ¼ 5.5 Hz, 1H,
Ar-H), 7.63 (d, J ¼ 8.8 Hz, 3H, Ar-H), 7.54–7.51 (m, 3H, Ar-
H), 7.47 (t, J ¼ 7.0 Hz, 1H, Ar-H), 7.34 (t, J ¼ 7.0 Hz, 1H, Ar-
H), 7.28 (d, J ¼ 5.2 Hz, 1H, Ar-H), 6.85–6.76 (m, 2H, Ar-H),
5.67 (dd, J ¼ 8.5, 4.0 Hz, 1H, Ar-H), 5.45 (dd, J ¼ 8.5, 3.7 Hz,
1H, Ar-H), 4.41 (t, J ¼ 11.6 Hz, 2H, CH2), 4.05 (t, J ¼ 5.2 Hz,
2H, CH2), 1.78–1.72 (m, 2H, CH2), 1.70–1.65 (m, 2H, CH2),
1.53–1.47 (m, 2H, CH2), 1.35–1.29 (m, 2H, CH2). MS: m/z calcd
1117.8; found 1118.0. Anal. Calcd for C46H33Br2F4IrN4O3: C,
49.43; H, 2.98; N, 5.01. Found: C, 50.30; H, 3.16; N, 4.86.
1
70% yield (3.46 g). H NMR (CDCl3, 500 MHz, ppm): d 7.46–
7.44 (m, 8H, Ar-H), 7.40 (t, J ¼ 7.6 Hz, 2H, Ar-H), 7.33–7.30
(m, 8H, Ar-H). 13C NMR (CDCl3, 125 MHz, ppm): d 140.38,
138.77, 135.56, 135.21, 133.78, 132.56, 130.66, 127.53. Ele-
mental Anal. Calcd. for C24H18Br2Si: C, 58.32%; H, 3.67%.
Found: C, 58.66%; H, 3.66%.
FIrpicOH (1)
The cyclometalated chloride-bridged dimer [(dfppy)2Ir(l-
Cl)]2 (101.1 mg, 0.081 mmol), 3-hydroxypyridine-2-carbox-
ylic acid (34.8 mg, 0.25 mmol) and sꢁodium carbonate (79.7
mg, 0.75 mmol) were refluxed at 120 C in a nitrogen atmos-
phere in 2-ethoxyethanol (7.5 mL) for 40 h. After cooling to
room temperature, a precipitate was filtered off and washed
with water and ether. The crude product was applied to col-
umn chromatography on silica gel, eluting with acetone–
dichloromethane mixture to provide the desired product in a
P36HCTPSi
Compounds M1 (109.4 mg, 0.22 mmol), M2 (107.5 mg, 0.22
mmol) and Pd(dppf)Cl2 (5.0 mg, 0.0061 mmol) were dis-
solved in THF (4 mL) and 1 M K2CO3 aqueous solution (1
mL). The reaction mixture was degassed and then stirred at
75 ꢁC for 3 days. At the end of the polymerization, phenyl-
boronic acid (5 mol %), and bromobenzene (5 mol %) were
added sequentially for end-capping. The mixture was poured
into water and extracted with dichloromethane then dried
over anhydrous magnesium sulfate. The solution was concen-
trated and purified by flash column chromatography to
remove the catalyst. After removal of the organic solvent, the
1
bright yellow solid in 65% yield (77.2 mg). H NMR (DMSO-
d6, 500 MHz, ppm): d 13.57 (s, 1H, OH), 8.51 (d, J ¼ 4.9 Hz,
1H, Ar-H), 8.30 (d, J ¼ 8.2 Hz, 1H, Ar-H), 8.26 (d, J ¼ 8.5 Hz,
1H, Ar-H), 8.09 (t, J ¼ 7.3 Hz, 1H, Ar-H), 8.05 (t, J ¼ 7.0 Hz,
1H, Ar-H), 7.69 (d, J ¼ 5.2 Hz, 1H, Ar-H), 7.64 (d, J ¼ 7.6 Hz,
1H, Ar-H), 7.54–7.50 (m, 2H, Ar-H), 7.36 (t, J ¼ 6.1 Hz, 1H,
Ar-H), 7.26 (d, J ¼ 4.0 Hz, 1H, Ar-H), 6.89–6.79 (m, 2H, Ar-
1860
INTERSCIENCE.WILEY.COM/JOURNAL/JPOLA