Macromolecules
Article
bottom flask equipped with magnetic stirrer was added TPE-diyne 7
(761 mg, 2 mmol), Pd(PPh3)2Cl2 (56 mg, 0.08 mmol), and CuI (30
mg, 0.16 mmol), followed by 20 mL of distilled THF, Et3N (0.59 mL,
4.2 mmol), and benzoyl chloride (2) (460 μL, 4 mmol) under
nitrogen. After stirring at 30 °C for 2 h, n-BuSH 3 (860 μL, 8 mmol)
and n-Bu3P (100 μL, 0.4 mmol) were injected. The mixture was stirred
for an additional 12 h, and 60 mL of water was then added. The
organic layer was extracted with dichloromethane (3 × 40 mL). The
solvent was removed under reduced pressure to afford crude product
which was purified by column chromatography on silica gel using
hexane/dichloromethane mixture (4:1) as eluent. A yellow solid was
obtained in 87% yield; Z/E = 85/15. IR (KBr thin film), v (cm−1):
3055, 3026, 2957, 2924, 2860, 1634, 1599, 1533, 1495, 1445, 1335,
mmol), and CuI (1.5 mg, 0.008 mmol) under nitrogen. 5 mL of freshly
distilled THF and anhydrous Et3N (30 μL, 0.21 mmol) were then
injected by syringes. After stirring at 30 °C for 2 h, 4,4′-
thiodibenzenethiol 12 (25 mg, 0.1 mmol) and n-Bu3P (12 μL, 0.04
mmol) were added to react for another 24 h at 30 °C under nitrogen.
The mixture was then added dropwise to 300 mL of methanol through
a cotton filter to precipitate the resultant polymer. The precipitate was
allowed to stand overnight and then filter. The polymer was washed
with methanol (3 × 30 mL) and dried under vacuum at 50 °C to a
constant weight. A pale brown powder was obtained in 74% yield. Mw:
5900. PDI: 1.42. IR (KBr thin film), v (cm−1): 3074, 3051, 3023, 2953,
2920, 2859, 2804, 1633, 1595, 1550, 1526, 1498, 1474, 1443, 1368,
1
1334, 1255, 1182, 1169, 1012, 944. H NMR (600 MHz, CDCl3), δ
1
(TMS, ppm): 7.95, 7.75, 7.60, 7.50, 7.38, 7.24−6.46, 6.37, 3.06.
P4: Into a 10 mL Schlenk tube equipped with magnetic stirrer was
placed with TPE-monoyne 5 (71 mg, 0.2 mmol), terephthaloyl
dichloride 9 (20 mg, 0.1 mmol), Pd(PPh3)2Cl2 (3 mg, 0.004 mmol),
and CuI (1.5 mg, 0.008 mmol) under nitrogen. 5 mL of freshly
distilled THF and anhydrous Et3N (30 μL, 0.21 mmol) were then
injected by syringes. After stirring at 30 °C for 2 h, 4,4′-
thiodibenzenethiol 12 (25 mg, 0.1 mmol) and n-Bu3P (12 μL, 0.04
mmol) were added to react for another 24 h at 30 °C under nitrogen.
The mixture was then added dropwise to 300 mL of methanol through
a cotton filter to precipitate the resultant polymer. The precipitate was
allowed to stand overnight and then filter. The product was washed
with methanol (3 × 30 mL) and dried under vacuum at 50 °C to a
constant weight. A yellow powder was obtained in 85% yield. Mw:
11 100. PDI: 2.17. IR (KBr thin film), v (cm−1): 3075, 3052, 3022,
2956, 2927, 2869, 1637, 1599, 1564, 1530, 1493, 1475, 1443, 1402,
1389, 1321, 1297, 1247, 1206, 1181, 1096, 1074, 1012, 956. 1H NMR
(600 MHz, CDCl3), δ (TMS, ppm): 8.10, 7.88, 7.65, 7.44, 7.25−6.75,
6.25.
1246, 1213, 1179, 1103, 1020, 955. H NMR (600 MHz, CDCl3), δ
(TMS, ppm): 7.97 (d, J = 7.7 Hz) + 7.74 (d, J = 7.8 Hz) (4H), 7.48
(m) + 7.34 (t, J = 7.5 Hz) (6H), 7.20−6.97 (m) + 6.58 (s) (20H),
2.79 (t, J = 7.4 Hz) + 2.35 (t, J = 7.4 Hz) (4H), 1.68 (m) + 1.42 (m) +
1.28 (m) (8H), 0.95 (m) + 0.83 (m) (6H). 13C NMR (150 MHz,
CDCl3), δ (TMS, ppm): 188.29, 163.52, 144.13, 143.04, 141.06,
138.71, 137.31, 132.16, 131.96, 131.46, 131.40, 131.35, 131.29, 131.26,
131.05, 128.63, 128.47, 128.29, 128.16, 128.08, 127.90, 127.69, 127.53,
127.43, 126.98, 119.57, 118.22, 32.61, 32.53, 31.55, 30.26, 22.13,
21.93, 13.73, 13.63. HRMS: m/z 769.3190 (M + H+ calcd 769.3168).
Elemental Analysis: C 81.50%, H 6.54%, S 7.98% (calcd C 81.21%, H
6.29%, S 8.34%).
Multicomponent Tandem Polymerizations. All the polymer-
ization procedures and manipulations were conducted under nitrogen
using standard Schlenk technique except the purification of the final
products.
A typical procedure of the MCTP to synthesize P1 is given below.
Into a 25 mL Schlenk tube equipped with magnetic stirrer was placed
with TPE-diyne 7 (76 mg, 0.2 mmol), terephthaloyl dichloride 9 (41
mg, 0.2 mmol), Pd(PPh3)2Cl2 (6 mg, 0.008 mmol), and CuI (6 mg,
0.032 mmol) under nitrogen. 5 mL of freshly distilled THF and
anhydrous Et3N (60 μL, 0.42 mmol) were then injected by syringes.
After stirring at 30 °C for 2 h, n-BuSH 3 (86 μL, 0.8 mmol) and n-
Bu3P (12 μL, 0.04 mmol) were injected to react for another 12 h at 30
°C under nitrogen. The mixture was then added dropwise to 300 mL
of methanol through a cotton filter to precipitate the polymer. The
precipitate was allowed to stand overnight and then filter. The product
was washed with methanol (3 × 30 mL) and dried under vacuum at 50
°C to a constant weight. A yellow solid was obtained in 96% yield. Mw:
57 900. PDI: 3.44. Stereoselectivity: Z/E = 76/24. IR (KBr thin film),
v (cm−1): 3053, 3024, 2955, 2924, 2864, 1632, 1528, 1493, 1400, 1242,
1217, 1042, 1011, 953. 1H NMR (600 MHz, CDCl3), δ (TMS, ppm):
8.01, 7.76, 7.20−6.95, 6.57, 2.79, 2.36, 1.67, 1.42, 1.28, 0.94, 0.83. 13C
NMR (150 MHz, CDCl3), δ (TMS, ppm): 187.48, 165.09, 144.27,
142.98, 141.29, 141.08, 137.14, 131.41, 131.29, 131.11, 128.29, 128.20,
127.94, 127.81, 127.47, 127.34, 127.05, 126.95, 126.81, 119.22, 32.72,
32.65, 31.50, 30.20, 22.13, 21.92, 13.80, 13.62.
ASSOCIATED CONTENT
■
S
* Supporting Information
Single crystal data for compound 6 (CCDC 1045141), 13C
NMR spectra of compounds 3, 4, 6−9, and P1, HR-MS spectra
of 4, 6, and 8, IR spectra of P2−4, thermogravimetric curve of
P1−P4, and negative photopattern of P1−P4. This material is
AUTHOR INFORMATION
■
Corresponding Authors
+852-2358-1594.
Notes
The authors declare no competing financial interest.
P2: Into a 25 mL Schlenk tube equipped with magnetic stirrer was
placed with TPE-diyne 7 (76 mg, 0.2 mmol), terephthaloyl dichloride
9 (41 mg, 0.2 mmol), Pd(PPh3)2Cl2 (6 mg, 0.008 mmol), and CuI (6
mg, 0.032 mmol) under nitrogen. 5 mL of freshly distilled THF and
anhydrous Et3N (60 μL, 0.42 mmol) were then injected by syringes.
After stirring at 30 °C for 2 h, p-toluenethiol 10 (99 mg, 0.8 mmol)
and n-Bu3P (12 μL, 0.04 mmol) were injected to react for another 12 h
at 30 °C under nitrogen. The mixture was then added dropwise to 300
mL of methanol through a cotton filter to precipitate the polymer. The
precipitate was allowed to stand overnight and then filter. The product
was washed with methanol (3 × 30 mL) and dried under vacuum at 50
°C to a constant weight. A yellow powder was obtained in 98% yield.
Mw: 59 100. PDI: 3.66. Stereoselectivity: Z/E = 63/37. IR (KBr thin
film), v (cm−1): 3052, 3022, 2956, 2922, 2855, 1635, 1598, 1560, 1530,
ACKNOWLEDGMENTS
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This work was partially supported by the National Science
Foundation of China (21404041, 21490573, 21490574), the
National Basic Research Program of China (973 Program;
2013CB834701), and the Research Grants Council of Hong
Kong (16305014, 604913, 602212, and 604711). B.Z.T. thanks
the support of the Guangdong Innovative Research Team
Program (201101C0105067115).
REFERENCES
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P3: Into a 10 mL Schlenk tube equipped with magnetic stirrer was
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benzoyl chloride 11 (37 mg, 0.2 mmol), Pd(PPh3)2Cl2 (3 mg, 0.004
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Macromolecules 2015, 48, 1941−1951