Alternating donor/acceptor repeat units in polythiophenes. Intramolecular charge transfer for reducing band gaps in fully substituted conjugated polymers

Journal of the American Chemical Society

Volumn 120, Issue 22, 1998, Pages 5355-

  Zhang, Qing T ^a   Tour, James M ^a  

^a UNIVERSITY OF SOUTH CAROLINA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; CHEMICAL BONDS; ELECTRONS; ENERGY GAP; LIGHT ABSORPTION; POLYMERIZATION;

INTRAMOLECULAR CHARGE TRANSFER; MOIETY; POLYTHIOPHENE; STEP GROWTH POLYMER; STILLE POLYMERIZATION; ULLMANN COUPLING;

ORGANIC POLYMERS;

POLYMER;

ARTICLE; ELECTRON TRANSPORT; ENERGY TRANSFER; MOLECULAR DYNAMICS; MOLECULAR INTERACTION; POLYMERIZATION; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 17344367297     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja972373e     Document Type: Article

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22. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
23. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
24. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
25. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
26. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
27. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
28. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
29. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
30. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
31. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
32. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
33. Although there have been a few reported examples of this alternating D/A strategy for chemically prepared processable polymers, none, to our knowledge, have employed multiple intensely donating and withdrawing groups as described here, and the reported corresponding band gap decreases have usually been considerably less intense. For chemical polymerization routes to D/A polyarylenes that had substitution on the acceptor moieties only, see: (a) Yamamoto, T.; Zhou, Z.-h.; Kanbara, T.; Shimura, M.; Kizu, K.; Maruyama, T.; Nakamura, Y.; Fukuda, T.; Lee, B.-L.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K.; Sasaki, S. J. Am. Chem. Soc. 1996, 118, 10389. (b) Yamamoto, T.; Kanbara, T.; Ooba, N.; Tomaru, S. Chem. Lett. 1994, 1709. For a chemical route to a D/A arylene-vinylene system, see: (c) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628. For some excellent electrochemical routes to D/A polymers (several of which afforded insoluble systems and none of which were fully substituted), see: (d) Demanze, F.; Yassar, A.; Garnier, F. Macromolecules 1996, 29, 4267. (e) Zhou, Z.-h.; Maruyama, T.; Kanbara, T.; Ikeda, T.; Ichimura, K.; Yamamoto, T.; Tokuda, K. J. Chem. Soc., Chem. Commun. 1991, 1210. (f) Havinga, E. E.; ten Hoeve, W.; Wynberg, H. Polym. Bull. 1992, 29, 119. (g) Lambert, T. L.; Ferraris, J. P. J. Chem. Soc., Chem. Commun. 1991, 752. (h) Ferraris, J. P.; Lambert, T. L. J. Chem. Soc., Chem. Commun. 1991, 1268. (i) Tamao, K.; Yamaguchi, S.; Ito, Y. J. Chem. Soc., Chem. Commun. 1994, 229. (j) Ho, H. A.; Brisset, H.; Frére, P.; Roncali, J. J. Chem. Soc., Chem. Commun. 1995, 2309. (k) Karikomi, M.; Kitamura, C.; Tanaka, S.; Yamashita, Y. J. Am. Chem. Soc. 1995, 117, 6791. (l) Tanaka, S.; Yamashita, Y. Synth. Met. 1993, 55-57, 1251. (m) Pagani, G.; Berlin, A.; Canavesi, A.; Schiavon, G.; Zecchin, S.; Zotti, G. Adv. Mater. 1996, 8, 819.
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