Macromolecules
Article
1
00 mg (0.12 mmol) of 2,2′-dibromo-3,3‴-didodecylquaterthiophene,
(4) Arias, A. C.; MacKenzie, J. D.; McCulloch, I.; Rivnay, J.; Salleo, A.
Chem. Rev. 2010, 110, 3.
(5) Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burrougher, J. H.;
Marks, R. N.; Taliani, C.; Bradley, D. D. C.; Dos Santos, D. A.; Bredas,
J. L.; Logdlund, M.; Salaneck, W. R. Nature 1999, 397, 121.
and 18.9 mg (0.12 mmol) of thiophen-3-ylmethyl acetate was stirred
in 2 mL of anhydrous dimethylacetamide for 3 h at 100 °C under a
nitrogen atmosphere. The reaction mixture was poured into an
aqueous solution of ethylenediaminetetraacetic acid disodium salt (pH
=
8), and the obtained suspension was stirred overnight at room
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6) Lo, S. C.; Burn, P. L. Chem. Rev. 2007, 107, 1097.
7) Dimitrakopoulos, C. D.; Malenfant, P. R. L. Adv. Mater. 2002, 14,
temperature. The precipitate was separated by filtration and washed
with 0.5 N HCl solution. The precipitate was dissolved in CHCl and
3
99.
reprecipitated in methanol. The copolymer was then purified by
Soxhlet extraction, first with methanol, then with hexane, and finally
with chloroform to yield pure polymer. Yield: 90%. M = 10772, M /
(
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8) Wen, Y.; Liu, Y. Adv. Mater. 2010, 22, 1331.
9) Cheng, Y.-J.; Yang, S.-H.; Hsu, C.-S. Chem. Rev. 2009, 109, 5868.
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(10) Thompson, B. C.; Frechet, J. M. J. Angew. Chem., Int. Ed. 2008,
1
M = 2.89. H NMR (400 MHz, CDCl ): δ 1.03 (b, 6H), 1.27−1.69
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4
7, 58.
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b, 40H), 2.16 (b, 1H), 2.79 (b, 4H), 5.21 (b, 2H), 7.05 (b, 4H), 7.15
b, 3H).
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1
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2
11) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. Rev. 2000,
00, 2537.
12) Du, Y.; Shen, S. Z.; Kefeng, C.; Casey, P. S. Prog. Polym. Sci
012, 37, 820.
Postfunctionalization of P1. To the solution of 37 mg (0.047
mmol) of P1 dissolved in 3 mL of anhydrous THF was added 0.9 mg
0.037 mmol) of NaH (60% in mineral oil) and the mixture stirred for
(
(13) Osaka, I.; McCullough, R. D. Acc. Chem. Res. 2008, 41, 1202.
half an hour under a nitrogen atmosphere. Then to the mixture a
solution of 20 mg (0.048 mmol) of 4-(((8-bromooctyl)oxy)methyl)-
(14) Beaujuge, P. M.; Frechet, J. M. J. Am. Chem. Soc. 2011, 133,
2
0009.
2
,2′-bi(1,3-dithiolylidene)/propargyl bromide in 0.2 mL of anhydrous
(15) Mishra, A.; Ma, C.-Q.; Bauerle, P. Chem. Rev. 2009, 109, 1141.
THF was added followed by the addition of DBU (2 μL) in a catalytic
amount. The mixture was stirred for 48 h under a nitrogen
atmosphere. The reaction mixture was poured then into 100 mL of
water and extracted 3−4 times from 40 mL of methylene chloride. The
combined organic layer was dried over Na SO and concentrated
(16) Skotheim, T. A.; Reynolds, J. In Conjugated Polymers: theory,
Synthesis, Properties, and Characterization, 3rd ed.; Blanchard, P.,
Leriche, P., Frere, P., Roncali, J., Eds.; Taylor & Francis Group:
London, 2006.
2
4
(
17) Purcell, S. T.; Garicia, N.; Binh, V. T.; Jones, L., II; Tour, J. M. J.
Am. Chem. Soc. 1994, 116, 11985.
18) Tour, J. M.; Jones, L.; Pearson, D. L.; Lamba, J. J. S.; Burgin, T.
under reduced pressure to yield red solid. The solid was then dissolved
in CHCl and reprecipitated in methanol 3−4 times. The polymer was
3
(
then purified by washing it with hexane and methanol, followed by
reprecipitating it again in methanol. The solid hence obtained was then
dried under vacuum for 24 h. P2: Yield: 66%. M = 11 857, M /M =
P.; Whitesides, G. M.; Allara, D. L.; Parikh, A. N.; Atre, S. V. J. Am.
Chem. Soc. 1995, 117, 9529.
(19) Liedberg, B.; Yang, Z.; Engquist, I.; Wirde, M.; Gelius, U.; Gotz,
G.; Bauerle, P.; Rummel, R. M.; Ziegler, C.; Gopel, W. J. Phys. Chem. B
1997, 101, 5951.
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2
5
2
.2. H NMR (400 MHz, CDCl ): δ 0.79 (b, 6H), 0.96−1.55 (b,
2H), 2.34 (b, 2H), 2.58 (b, 2H), 3.18 (b, 2H), 3.25 (b, 2H), 3.76 (b,
3
H), 3.88 (b, 2H), 5.81 (b, 1H), 5.94 (b, 2H), 6.69−6.95 (b, 7H). P3:
Yield: 80%. M = 12228, M /M = 2.41. 1H NMR (400 MHz,
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(20) Taniguchi, S.; Minamoto, M.; Matsushita, M. M.; Sugawara, T.;
Kawada, Y.; Bethell, D. J. Mater. Chem. 2006, 16, 3459.
(21) Huang, W.; Masuda, G.; Maeda, S.; Tanaka, H.; Ogawa, T.
Chem.Eur. J. 2006, 12, 607.
CDCl ): δ 0.87 (b, 6H), 1.26−1.69 (b, 40H), 2.51 (b, 1H), 2.77 (b,
3
4H), 4.28 (b, 2H), 4.70 (b, 2H), 7.07 (b, 4H), 7.14 (b, 3H).
ASSOCIATED CONTENT
(22) Barik, S.; Valiyaveettil, S. Macromolecules 2008, 41, 6376.
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23) Olenyuk, B.; Whiteford, J. A.; Fechtenkotter, A.; Stang, P. J.
Nature 1999, 398, 796.
24) Nie, Z.; Fava, D.; Kumacheva, E.; Zou, S.; Walker, G. C.;
Rubinstein, M. Nat. Mater. 2007, 6, 609.
25) (a) Lu, S.; Liu, T.; Ke, L.; Ma, D. G.; Chua, S. J.; Huang, W.
* Supporting Information
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AUTHOR INFORMATION
Macromolecules 2005, 38, 8494. (b) Zahn, S.; Swager, T. M. Angew.
Chem., Int. Ed. 2002, 41, 4225. (c) Lee, M.; Cho, B. K.; Zin, W. C.
Chem. Rev. 2001, 101, 2869.
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*
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26) Roncali, J.; Li, H. S.; Garreau, R.; Garnier, F.; Lemaire, M. Synth.
Met. 1990, 36, 267.
(27) Bauerle, P.; Scheib, S. Adv. Mater. 1993, 5, 848.
(28) Bauerle, P.; Gotz, G.; Hiller, M.; Scheib, S.; Fischer, T.;
Present Address
Korea Research Institute of Chemical Technology (KRICT),
Division of Chemical R&BD, Ulsan 681-310, Republic of
Korea.
§
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̈
̈
Segelbacher, U.; Bennati, M.; Grupp, A.; Mehring, M.; Stoldt, M.;
Seidel, C.; Geiger, F.; Schweizer, H.; Umbach, E.; Schmelzer, M.; Roth,
S.; Egelhaaf, H. J.; Oelkrug, D.; Emele, P.; Port, H. Synth. Met. 1993,
Notes
The authors declare no competing financial interest.
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1, 71.
29) Scheib, S.; Bau
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(
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erle, P. J. Mater. Chem. 1999, 9, 2139.
ACKNOWLEDGMENTS
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We thank Mingling Yeh and Dr. Weiguo Huang for assistance
with physical characterizations and depositions. We gratefully
acknowledge funding from the Department of Energy Office of
Basic Energy Sciences, Grant DE-FG02-07ER46465, for
funding the polymer synthesis, physical studies, and thermo-
electric investigations.
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dx.doi.org/10.1021/ma3019365 | Macromolecules XXXX, XXX, XXX−XXX