Recent advances in polythiophene synthesis by palladium-catalyzed cross-coupling reactions

Current Organic Chemistry

Volumn 15, Issue 18, 2011, Pages 3263-3290

  Hoyos, Mario ^a   Turner, Michael L ^b   Navarro, Oscar ^a  

^a UNIVERSITY OF HAWAII   (United States)

^b UNIVERSITY OF MANCHESTER   (United Kingdom)

Author keywords

C C and C X bond formation; Palladium catalyzed cross coupling reactions; Polymerization; Polythiophenes; Sonogashira; Stille

Indexed keywords

CATALYSIS; SYNTHESIS (CHEMICAL);

BOND FORMATION; C-C AND C-X BOND FORMATION; CATALYST LOADINGS; FUNCTIONALS; HIGHER EFFICIENCY; ORGANIC CHEMISTRY; PALLADIUM-CATALYZED CROSS-COUPLING REACTIONS; POLYMERIZATION PROCESS; SONOGASHIRUM; STILLE;

POLYMERIZATION;

EID: 80052476041     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527211797247996     Document Type: Review

References (157)

1. Meyer, V. Ueber den Begleiter des Benzols im Steinkohlentheer. Ber. Deutsch. Chem. Ges. 1883, 16, 1465-1478.
2. Yamamoto, T.; Sanechika, K.; Yamamoto, A. Preparation of thermostable and electric-conducting poly(2,5-thienylene. J. Polym. Sci., Polym. Lett. Ed. 1980, 18, 9-12.
3. Lin, J. W. P.; Dudek, L. P. Synthesis and properties of poly(2,5-thienylene. J. Polym. Sci., Polym. Chem. Ed., 1980, 18, 2869-2873.
4. Torsi, L.; Tafuri, A.; Cioffi, N.; Gallazzi, M. C.; Sassella, A.; Sabbatini, L.; Zambonin, P. G. Regioregular polythiophene field-effect transistors employed as chemical sensors. Sens. Actua. B Chem. 2003, 93, 257-262.
5. Anderson, M. R.; Thomas, O.; Mammo, W.; Svensson, M.; Theander, M.; Inganas O. Substituted polythiophenes designed for optoelectronic devices and conductors. J. Mater. Chem. 1999, 9, 1933-1940.
6. McQuade, D. T.; Pullen, A. E.; Swager, T. M. Conjugated polymer-based chemical sensors. Chem. Rev. 2000, 100, 2537-2574.
7. Liu, J.; Tanaka, T.; Sivula, K.; Alivisatos, A. P.; Fréchet, J. M. J. Employing end-functional polythiophene to control the morphology of nanocrystal - Polymer composites in hybrid solar cells. J. Am. Chem. Soc. 2004, 126, 6550-6551.
8. Gunes, S.; Neugebauer, H.; Sariciftci, N.S. Conjugated polymer-based organic solar cells. Chem Rev. 2007, 107, 1324-1338.
9. Kim, J. Y.; Lee, K.; Coates, N. E.; Moses, D.; Nguyen, T. Q.; Dante, M.; Heeger, A.J. Efficient tandem polymer solar cells fabricated by all-solution processing. Science 2007, 317, 222-225.
10. Perepichka, I. F.; Perepichka, D. F.; Meng, H.; Wudl, F. Light-emitting polythiophenes. Adv. Mater. 2005, 17, 2281-2305.
11. Zaumseil, J.; Sirringhaus, H. Electron and ambipolar transport in organic field-effect transistors. Chem. Rev. 2007, 107, 1296-1323.
12. Sivula, K.; Luscombe, C. K.; Thompson, B. C.; Fréchet, J. M. J. Enhancing the thermal stability of polythiophene:fullerene solar cells by decreasing effective polymer regioregularity. J. Am. Chem. Soc. 2006, 128, 13988-13989.
13. Yang, C.; Hu, J. G.; Heeger, A. J. Molecular Structure and Dynamics at the Interfaces within Bulk Heterojunction Materials for Solar Cells. J. Am. Chem. Soc. 2006, 128, 12007-12013.
14. Kim, K.; Liu, J.; Namboothiry, M. A. G.; Carroll, D.L. Roles of donor and acceptor nanodomains in 6% efficient thermally annealed polymer photovoltaics. Appl. Phys. Lett. 2007, 90, 163511-163513.
15. Li, G.; Shrotriya, V.; Huang, J.; Yao, Y.; Moriarty, T.; Emery, K.; Yang, Y. High-efficiency solution processable polymer photovoltaic cells by selforganization of polymer blends. Nat. Mater. 2005, 4, 864-868.
16. Ballauff, M. Stiff-Chain Polymers-Structure, Phase Behavior, and Properties. Angew. Chem. Int. Ed. Eng. 1989, 28, 253-267.
17. McCullough, R. D. The Chemistry of Conducting Polythiophenes: from Synthesis to Self-Assembly to Intelligent Materials. Handbook of Oligo- and Polythiophenes, Ed. D. Fichou, Wiley-VCH:New York, 1999; Chapter 1, 1-44.
18. Jeffries-El, M.; McCullough, R. D. Regioregular Polythiophenes The Handbook of Conducting Polymers, 3rd Edition, Ed. Skotheim T. A.; Reynolds J. R., Taylor&Francis Group, Florida, 2007; Chapter 9, 1-49.
19. McCullough, R. D.; Tristram-Nagle, S. P.; Williams, S. P.; Lowe, R. D.; Jayaraman, M. Self-orienting head-to-tail poly(3-alkylthiopbenes): New insights on structure-property relationships in conducting polymers. J. Am. Chem. Soc. 1993, 115, 4910-4911.
20. McCullough, R. D. The chemistry of conducting polythiophenes. Adv. Mater. 1998, 10, 93-116.
21. Elsenbaumer, R. L.; Jen, K. Y.; Oboodi, R. Processible and environmentally stable conducting polymers. Synth. Met., 1986, 15, 169-174.
22. Kumada, M. Nickel and palladium complex catalyzed cross-coupling reactions of organometallic reagents with organic halides. Pure Appl. Chem. 1980, 52, 669-679.
23. Corriu, R. J. P.; Masse, J. P. Activation of Grignard reagents by transitionmetal complexes. A new and simple synthesis of trans-stilbenes and polyphenyls. J. Chem. Soc. Chem. Comm. 1972, 144-146.
24. Diederich, F.; Stang, P. J. Metal-Catalyzed Cross-Coupling Reactions. Wiley-VCH: Weinheim 1998.
25. Genet, J. P.; Savignac, M. Recent developments of palladium(0) catalyzed reactions in aqueous medium. J. Organomet. Chem. 1991, 576, 305-317.
26. Boudier, A.; Bromm, L. O.; Lotz, M.; Knochel P. New applications of polyfunctional organometallic compounds in organic synthesis. Angew. Chem. Int. Ed. 2000, 39, 4414-4435.
27. Hassan, J.; Sevignon, M.; Gozzi, C.; Schultz, E.; Lemaire, M. Aryl-aryl bond formation one century after the discovery of the Ullmann reaction. Chem. Rev. 2002, 102, 1359-1470.
28. McCullough, R. D.; Lowe, R. D. Enhanced electrical conductivity in regioselectively synthesized poly(3-alkylthiophenes. J. Chem. Soc. Chem. Commun. 1992, 1, 70-72.
29. McCullough, R. D.; Lowe, R. D.; Jayaraman M.; Anderson D. L. Design, synthesis, and control of conducting polymer architectures: Structurally homogeneous poly(3-alkylthiophenes. J. Org. Chem. 1993, 58, 904-912.
30. Chen, T. A.; Rieke, R. D. The first regioregular head-to-tail poly(3- hexylthiophene-2,5-diyl) and a regiorandom isopolymer: nickel versus palladium catalysis of 2(5)-bromo-5(2)-(bromozincio)-3-hexylthiophene polymerization. J. Am. Chem. Soc. 1992, 114, 10087-10088.
31. Street, G. B.; Clarke, T. C. Conducting polymers: a review of recent work. IBM J. Res. Dev. 1981, 25, 51-57.
32. Schopf, G.; Koßmehl, G. Polythiophenes-electrically conductive polymers. Adv. Polym. Sci. 1997, 129, 1-166.
33. Roncali, J. Conjugated poly(thiophenes): Synthesis, functionalization, and applications. Chem. Rev. 1992, 92, 711-738.
34. Roncali, J. Synthetic principles for bandgap control in linear Π-conjugated systems. Chem. Rev. 1997, 97, 173-205.
35. Reddinger, J. L.; Reynolds, J. R. Molecular engineering of Π-conjugated polymers. Adv. Polym. Sci. 1999, 145, 57-122.
36. Perepichka, I. F.; Perepichka, D. F. Handbook of Thiophene-Based Materials: Applications in Organic Electronics and Photonics. John Wiley&Sons, Ltd: U.K, 2009.
37. Tamao, K.; Miyaura, N. Polyester and ester functionalized dendrimers. Top. Curr. Chem. 2002, 210, 1-9.
38. Negishi, E. I.; Valente, L. F.; Kobayashi, M. Palladium-catalyzed crosscoupling reaction of homoallylic or homopropargylic organozincs with alkenyl halides as a new selective route to 1,5-dienes and 1,5-enynes [36]. J. Chem. Soc. 1980, 102, 3298-3299.
39. Knochel, P.; Singer, R. D. Preparation and reactions of polyfunctional organozinc reagents in organic synthesis. Chem. Rev. 1993, 93, 2117-2188.
40. Rieke, R. D.; Hanson, M. V. New organometallic reagents using highly reactive metals. Tetrahedron report number 413. Tetrahedron 1997, 53, 1925-1956.
41. Heck, R. F.; Nolley, Jr., J.P. Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides. J. Org. Chem. 1972, 37, 2320-2322.
42. Stille, J. K. The Palladium-Catalyzed Cross-Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)]. Angew. Chem. Int. Ed. Eng. 1986, 25, 508-524.
43. Suzuki, A. Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995-1998. J. Organomet. Chem. 1999, 576, 147-168.
44. Kosugi, M.; Sasazawa, K.; Shimizu, Y.; Migita, T. Reactions of allyltin compounds iii. Allylation of aromatic halides with allyltributyltin in the presence of tetrakis(triphenylphosphine) palladium(0). Chem. Lett. 1977, 301.
45. Stille, J. K.; Lau, K. S. Y. Mechanisms of oxidative addition of organic halides to Group 8 transition-metal complexes. Acc. Chem. Res. 1977, 10, 434-442.
46. Farina, V.; Krishnamurthy, V.; Scott, W. J. The Stille Reaction, Org. React. 1997, 50, 1.
47. Kosugi, M.; Ohya, T.; Migita, T. Glutamate receptor antagonists. Bull. Chem. Soc. Jap. 1983, 56, 3855-3856.
48. Casado, A. L.; Espinet, P. Mechanism of the Stille Reaction. 1. The Transmetalation Step. Coupling of R1I and R2SnBu3 Catalyzed by trans-[PdR1IL2] (R1 = C6Cl2F3; R2 = Vinyl, 4-Methoxyphenyl; L = AsPh3). J. Am. Chem. Soc. 1998, 120, 8978-8985.
49. Espinet, P.; Echavarren, A. M. The mechanisms of the Stille reaction. Angew. Chem. Int. Ed. 2004, 43, 4704-4734.
50. Huang, Y; Wang, Y.; Sang, G.; Zhou, E.; Huo, L.; Liu, Y.; Li, Y. Polythiophene Derivative with the Simplest Conjugated-Side-Chain of Alkenyl: Synthesis and Applications in Polymer Solar Cells and Field-Effect Transistors. J. Phys. Chem. B 2008, 112, 13476-13482.
51. Hou, J.; Tan, Z.; He, Y.; Yang, C.; Li, Y. Branched Poly(thienylene vinylene)s with Absorption Spectra Covering the Whole Visible Region. Macromolecules 2006, 39, 4657-4662.
52. Hou, J.; Tan, Z.; Yan, Y.; He, Y.; Yang, C.; Li, Y. Synthesis and Photovoltaic Properties of Two-Dimensional Conjugated Polythiophenes with Bi(thienylenevinylene) Side Chains. J. Am. Chem. Soc. 2006, 128, 4911-4916.
53. Yu, C.-Y.; Ko, B.-T.; Ting, C.; Chen, C.-P. Two-dimensional regioregular polythiophenes with conjugated side chains for use in organic solar cells. Solar Energy Materials & Solar Cells 2009, 93, 613-620.
54. He, Y.; Wu, W; Zhao, G.; Liu, Y.; Li, Y. Poly(3,6-dihexyl-thieno[3,2- b]thiophene vinylene): Synthesis, Field-Effect Transistors, and Photovoltaic Properties. Macromolecules 2008, 41, 9760-9766.
55. Smith, J. R.; Campbell, S. A.; Ratcliffe, N. M.; Dunleavy M. Polyheterocycles containing alkene spacer linkages Part I. Synthesis and electropolymerization of 3-styrylthiophenes. Synth. Met. 1994, 63, 233-243.
56. Hou, J.; Huo, L.; He, C.; Yang, C.; Li, Y. Synthesis and Absorption Spectra of Poly(3-(phenylenevinyl)thiophene)s with Conjugated Side Chains. Macromolecules 2006, 39, 594-603.
57. Loewe, R. S.; Khersonsky, S. K.; McCullough, R. D. A Very Simple Method to Prepare Head-to-Tail Coupled, Regioregular Poly(3-alkylthiophenes) Using Grignard Metathesis. Adv. Mater. 1999, 11, 250-253. 47.
58. Wan, M.; Sang, G.; Zou, Y.; Tan, S.; Li, Y. A Polythiophene Derivative with Dioctyloxyltriphenylamine -Vinylene Conjugated Side Chain: Synthesis, Hole Mobility and Photovoltaic Property. J. of Appl. Polym. Sci. 2009, 113, 1415-1421.
59. Sang, G.; Zhou, E.; Huang, Y.; Zou, Y.; Zhao, G.; Li, Y. Incorporation of thienylenevinylene and triphenylamine moieties into polythiophene side chains for all-polymer photovoltaic applications. J. Phys. Chem. C 2009, 113, 5879-5885.
60. Zou, Y.; Sang, G.; Wan, M.; Tan, S.; Li, Y. Synthesis, Electrochemical and Photovoltaic Properties of Multi-Armed Polythiophenes with Triphenylamine Trivinylene as Conjugated Linker. Macromol. Chem. Phys. 2008, 209, 1454-1462.
61. Zou, Y.; Sang, G.; Wu, W.; Yunqui, L.; Li, Y. A Polythiophene Derivative with Octyloxyl Triphenylamine-vinylene Conjugated Side Chain: Synthesis and Its Applications in Field-Effect Transistor and Polymer Solar Cell. Synt. Met. 2009, 159, 182-187.
62. Tan, Z.; Zhou, E.; Yang, Y.; Youjun, H.; Yang, C.; Li, Y. Synthesis, characterization and photovoltaic properties of thiophene copolymers containing conjugated side-chain. European Polymer Journal 2007, 43, 855-861.
63. Hittinger, E.; Kokil, A.; Weder, C. Synthesis and Characterization of Cross- Linked Conjugated Polymer Milli-, Micro-, and Nanoparticles. Angew. Chem., Int. Ed. 2004, 43, 1808-1811.
64. Weder, C. Synthesis, processing and properties of conjugated polymer networks. Chem. Commun. 2005, 5378-5389.
65. Zhou, E.; Tan, Z.; Yang, C.; Li, Y. Linking polythiophene chains through conjugated bridges: a way to improve charge transport in polymer solar cells. Macromol. Rapid Commun. 2006, 27, 793-798.
66. Zhou, E.; Tan, Z.; Yang, Y.; Huo, L.; Zou, Y.; Yang, C.; Li, Y. Synthesis, Hole Mobility, and Photovoltaic Properties of Cross-Linked Polythiophenes with Vinylene-Terthiophene-Vinylene as Conjugated Bridge. Macromolecules 2007, 40, 1831-1837.
67. Lu, K.; Sun, X.; Liu, Y.; Di, C.; Xi, H.; Yu, G.; Gao, X.; Du, C. Linking polythiophene chains with vinylene-bridges: A way to improve charge transport in polymer field-effect transistors. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 1381-1392.
68. Ohshita, J.; Kimura, K.; Lee, K.-H.; Kunai, A.; Kwak, Y.-W.; Son, E.-C.; Knugi, Y. Synthesis of silicon-bridged polythiophene derivatives and their applications to EL device materials. J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 4588-4596.
69. Hou, J.; Chen, H.-Y.; Zhang, S.; Li, G.; Yang, Y. Synthesis, Characterization, and Photovoltaic Properties of a Low Band Gap Polymer Based on Silole- Containing Polythiophenes and 2,1,3-Benzothiadiazole. J. Am. Chem. Soc. 2008, 130, 16144-16145.
70. Hou, J.; Park, M.-H.; Zhang, S.; Yao, Y.; Chen, L.-M.; Li, J-H; Yang, Y. Bandgap and Molecular Energy Level Control of Conjugated Polymer Photovoltaic Materials Based on Benzo[1,2-b:4,5-b']dithiophene. Macromolecules 2008, 41, 6012-6018.
71. Liao, L.; Dai, L.; Smith, A.; Durstock, M.; Lu, J.; Ding, J.; Tao, Y. Photovoltaic- Active Dithienosilole-Containing Polymers. Macromolecules 2007, 40, 9406-9412.
72. Wang, E; Wang, L.; Lan, L.; Luo, C.; Zhuang, W.; Peng, J.; Cao, Y. High performance polymer heterojunction solar cells of a polysilafluorene derivative. Appl. Phys. Lett. 2008, 92, 0333071-0333073.
73. Hou, J.; Chenm, T. L.; Zhang, S.; Chen, H.-Y.; Yang, Y. Poly[4,4-bis(2- ethylhexyl)cyclopenta[2,1-b;3,4-b']dithiophene-2,6-diyl-alt-2,1,3- benzoselenadiazole-4,7-diyl], a New Low Band Gap Polymer in Polymer Solar Cells. J. Phys. Chem. C 2009, 113, 1601-1605.
74. Zhu, Z.; Waller, D.; Gaudiana, R.; Morana, M.; Mühlbacher, D.; Scharber, M.; Brabec, C. Panchromatic Conjugated Polymers Containing Alternating Donor/Acceptor Units for Photovoltaic Applications. Macromolecules 2007, 40, 1981-1986.
75. Ogawa, K.; Rasmussen, S. C. N-Functionalized Poly(dithieno[3,2-b:2',3'- d]pyrrole)s: Highly Fluorescent Materials with Reduced Band Gaps. Macromolecules 2006, 39, 1771-1778.
76. Huang, T.-H.; Lin, J.-T.; Chen, L.-Y.; Lin, Y.-T.; Wu, C.-C. Dipolar Dibenzothiophene S,S-Dioxide Derivatives Containing Diarylamine: Materials for Single-Layer Organic Light-Emitting Devices. Adv. Mater. 2006, 18, 602-606.
77. Chan, L.-H.; Lee, Y.-D.; Chen, C.-T. Synthesis and Characterization of 3,4- Diphenylmaleimide Copolymers That Exhibit Orange to Red Photoluminescence and Electroluminescence. Macromolecules 2006, 39, 3262-3269.
78. Perepichka, I. I.; Perepichka, I. F.; Bryce, M. R.; Palsson, L.-O. Dibenzothiophene- S,S-dioxide-fluorene co-oligomers. Stable, highly-efficient blue emitters with improved electron affinity. Chem. Commun. 2005, 3397-3399.
79. Melucci, M.; Favaretto, L.; Barbarella, G.; Zanelli, A.; Camaioni, N.; Mazzeo, M.; Gigli, G. Synthesis and electrooptical properties of a red emitting branched polymer containing V-shaped oligothiophene-S,S-dioxides as repeating units. Tetrahedron 2007, 63, 11386-11390.
80. Vanormelingen, W.; Van den Bergh, K.; Verbiest, T.; Koeckelberghs, G. Conformational Transitions in Chiral, Gallic Acid-Functionalized Poly(dithienopyrrole): A Comparative UV-vis and CD Study. Macromolecules 2008, 41, 5582-5589.
81. Zhou, E.; Nakamura, M.; Nishizawa, T.; Zhang, Y.; Wei, Q.; Tajima, K.; Yang, C.; Hashimoto, K. Synthesis and Photovoltaic Properties of a Novel Low Band Gap Polymer Based on N-Substituted Dithieno[3,2-b:2',3'- d]pyrrole. Macromolecules 2008, 41, 8302-8305.
82. Mishra, S. P.; Palai, A. K.; Srivastava, R.; Kamalasanan, M. N.; Patri, M. Dithieno[3,2-b:2',3'-d]pyrrole-alkylthiophene-benzo[c][1,2,5]thiadiazolebased highly stable and low band gap polymers for polymer light-emitting dioses. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 6514-6525.
83. Liang, F.; Jianping, L. J.; Ding, J.; Movileanu, R.; Tao, Y. Design and Synthesis of Alternating Regioregular Oligothiophenes/Benzothiadiazole Copolymers for Organic Solar Cells. Macromolecules 2009, 42, 6107-6114.
84. Bundgaard, E.; Krebs, F. C. Low-Band-Gap Conjugated Polymers Based on Thiophene, Benzothiadiazole, and Benzobis(thiadiazole. Macromolecules 2006, 39, 2823-2831.
85. Qin, Y.; Kim, J. Y.; Frisbie, C. D.; Hillmyer, M. A. Distannylated Isothianaphthene: A Versatile Building Block for Low Bandgap Conjugated Polymers. Macromolecules 2008, 41, 5563-5570.
86. Zhan, X.; Tan, Z.; Domercq, B.; An, Z.; Zhang, X.; Barlow, S.; Li, Y.; Zhu, D.; Kippelen, B.; Marder, S.R. A High-Mobility Electron-Transport Polymer with Broad Absorption and Its Use in Field-Effect Transistors and All- Polymer Solar Cells. J. Am. Chem. Soc. 2007, 129, 7246-7247.
87. Liu, Y.; Yang, C.; Li, Y.; Li, Y.; Wang, S.; Zhuang, J.; Liu, H.; Wang, N.; He, X.; Li, Y.; Zhu, D. Synthesis and Photovoltaic Characteristics of Novel Copolymers Containing Poly(phenylenevinylene) and Triphenylamine Moieties Connected at 1,7 Bay Positions of Perylene Bisimide. Macromolecules 2005, 38, 716-721.
88. Guo, X.; Watson, M. D. Conjugated Polymers from Naphthalene Bisimide. Org. Lett. 2008, 10, 5333-5336.
89. Nehls, B. S.; Asawapirom, U.; Fulder, S.; Preis, E.; Farrell, T.; Scherf U. Semiconducting Polymers via Microwave-Assisted Suzuki and Stille Cross- Coupling Reactions. Adv. Funct. Mater. 2004, 14, 354-356.
90. Galbrecht, F.; Bünnagel, T. W.; Scherf, U.; Farrell, T. Microwave-assisted preparation of semiconducting polymers. Macrom. Rapid. Commun. 2007, 28, 387-394.
91. Tierney, S.; Heeney, M.; McCulloch I. Microwave-assisted synthesis of polythiophenes via the Stille coupling. Synth. Met. 2005, 148, 195-198.
92. McCulloch, I.; Heeney, M.; Baliley, C.; Genevicius, K.; Macdonald, I.; Shkunov, M.; Sparrowe, D.; Tierney, S.; Wagner, R.; Chabinyc, M. L.; Kline R. J.; McGehee M. D.; Toney M. F. Liquid-crystalline semiconducting polymers with high charge-carrier mobility. Nat. Mater. 2006, 5, 328-333.
93. Moulé, A. J.; Tsami, A.; Bünnagel, T. W.; Forster, M.; Kronenberg, N. M.; Scharber, M.; Koppe, M.; Morana, M.; Brabec, C. J.; Meerholz, K.; Scherf, U. Two Novel Cyclopentadithiophene-Based Alternating Copolymers as Potential Donor Components for High-Efficiency Bulk-Heterojunction-Type Solar Cells. Chem. Mater. 2008, 20, 4045-4050.
94. Coppo, P.; Turner, M. L. Cyclopentadithiophene based electroactive materials. J. Mater. Chem. 2005, 15, 1123-1133.
95. Muhlbacher, D.; Scharber, M.; Morana, M.; Zhu, Z. G.; Waller, D.; Gaudiana, R.; Brabec, C. High Photovoltaic Performance of a Low-Bandgap Polymer. Adv. Mater. 2006, 18, 2931
96. Peet, J.; Kim, J. Y.; Coates, N. E.; Ma, W. L.; Moses, D.; Heeger, A. J.; Bazan, G. C. Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols. Nat. Mater. 2007, 6, 497-500.
97. Wong, K. T.; Chao, T. C., Chi, L. C.; Chu, Y. Y.; Balaiah, A.; Chiu, S. F.; Liu, Y. H.; Wang, Y. Syntheses and Structures of Novel Heteroarene-Fused Coplanar Π-Conjugated Chromophores. Org. Lett. 2006, 8, 5033-5036.
98. Chan, S.-H.; Chen, C.-P.; Chao, T.-C.; Ting, C.; Lin, C.-S.; Ko, B.-T. Synthesis, Characterization, and Photovoltaic Properties of Novel Semiconducting Polymers with Thiophene-Phenylene-Thiophene (TPT) as Coplanar Units. Macromolecules 2008, 41, 5519-5526.
99. Chen, C-P.; Chan, S-H.; Chao, T-C.; Ting, C., Ko, B.-T. Poly(Thiophene- Phenylene-Thiophene) Derivatives with Broaden Absorption Spectra for Use in High-Performance Bulk-Heterojunction Polymer Solar Cells. J. Am. Chem. Soc. 2008, 130, 12828-12833.
100. Osaka, I.; Sauvé, G.; Zhang, R.; Kowalewski, T.; McCullough, R. D. Novel Thiophene-Thiazolothiazole Copolymers for Organic Field-Effect Transistors. Adv. Mater. 2007, 19, 4160-4165.
101. Liang, Y.; Feng, D.; Guo, J.; Szarko, J. M.; Ray, C.; Chen, L. X.; Yu, L. Regioregular Oligomer and Polymer Containing Thieno[3,4-b]thiophene Moiety for Efficient Organic Solar Cells. Macromolecules 2009, 42, 1091-1098.
102. Sang, G.; Zou, Y.; Li, Y. Two Polythiophene Derivatives Containing Phenothiazine Units: Synthesis and Photovoltaic Properties. J. Phys. Chem. C 2008, 112, 12058-12064.
103. Zou, Y. P.; Wu, W. P.; Sang, G. Y.; Yang, Y.; Liu, Y. Q.; Li, Y. F. Polythiophene Derivative with Phenothiazine-Vinylene Conjugated Side Chain: Synthesis and Its Application in Field-Effect Transistors. Macromolecules 2007, 40, 7231-7237.
104. Zhao, C.; Zhang Y.; Ng, M.-K. Derivatives of 4,9-Dihydro-s-indaceno[1,2- b:5,6-b']dithiophene-4,9-dione: Synthesis and Properties. J. Org. Chem. 2007, 72, 6364-6371.
105. Zhao, C.; Chen, X.; Zhang, Y.; Ng M.-K. 4,9-Dihydro-s-indaceno[1,2-b:5,6- b']dithiophene-4,9-dione functionalized copolymers for organic photovoltaic devices. J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 2680-2688.
106. Peng, Q.; Park, K.; Lin, T.; Durstock, M.; Dai, L. Donor-Acceptor Conjugated Copolymers for Photovoltaic Applications: Tuning the Open-Circuit Voltage by Adjusting the Donor/Acceptor Ratio. J. Phys. Chem. B 2008, 112, 2801-2808
107. Murphy, A. R.; Fréchet J. M. J.; Chang, P.; Lee, J.; Subramanian, V. J. Organic Thin Film Transistors from a Soluble Oligothiophene Derivative Containing Thermally Removable Solubilizing Groups. J. Am. Soc. Chem. 2004, 126, 1596-1597
108. Liu J.; Kadnikova E. N.; Liu Y.; McGehee M. D.; Frèchet J. M. J. Small- Molecule Dimerization Inhibitors of Wild-Type and Mutant HIV Protease: A Focused Library Approach. J. Am. Soc. Chem. 2004, 126, 9486-9487.
109. Dieck, H. A.; Heck, R. F. Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives. J. Organomet. Chem. 1975, 93, 259-263.
110. Cassar, I. Synthesis of aryl- and vinyl-substituted acetylene derivatives by the use of nickel and palladium complexes. J. Organomet. Chem. 1975, 93, 253-255.
111. Sonogashira, K.; Tohda, Y.; Hagihara, N. A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Lett. 1975, 16, 4467-4470.
112. Dieck, H. A.; Heck, R. F. Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives. J. Organomet. Chem. 1975, 93, 259-263.
113. Sonogashira, K.; Tohda, Y.; Hagihara, N. A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetraedron Lett. 1975, 16, 4467-4470.
114. Zou, Y.; Tan, Z.; Huo, L.; Li, Y. A phenylenevinylene-thiophene- phenyleneethynylene copolymer: synthesis, characterization, and photovoltaic properties. Polym. Adv. Technol. 2008, 19, 865-871.
115. Lu, S. L.; Yang, M. J.; Luo, J.; Cao, Y.; Bai, F. L. Novel Alternating Dioctyloxyphenylene Vinylene-Benzothiadiazole Copolymer: Synthesis and Photovoltaic Performance. Macromol. Chem. Phys. 2005, 206, 664-671.
116. Ashraf, R.S., Shahid, M.; Klemm, E.; Al-Ibrahim, M.; Sensfuss, S. Thienopyrazine- Based Low-Bandgap Poly(heteroaryleneethynylene)s for Photovoltaic Devices. Macromol. Rapid Commun. 2006, 27, 1454-1459.
117. Pilzak, G.S.; Van Gruijthuijsen, K.; Van Doorn, R.H.; Van Lagen, B.; Sudhölter, E.J.R.; Zuilhof, H. Hybrid Conjugated Organic Oligomers Consisting of Oligodiacetylene and Thiophene Units: Synthesis and Optical Properties. Chem. Eur. J. 2009, 15, 9085-9096.
118. Pilzak, G. S.; Van Lagen, B.; Hendrikx, C. C. J.; Sudhölter, E. J. R.; Zuilhof, H. Synthesis and Optical Properties of all-trans-Oligodiacetylenes. Chem. Eur. J. 2008, 14, 7939-7950.
119. Rupert, B. J.; Mitchell, W. J.; Ferguson, A. J.; Köse, M. E.; Rance, W. L.; Rumbles, G.; Ginley, D. S.; Shaheen, S. E.; Kopidakis, N. Low-Bandgap Thiophene Dendrimers for Improved Light Harvesting. Journal of Materials Chemistry J. Mater. Chem. 2009, 19, 5311-5324.
120. Mitchell, W. J.; Ferguson A. J.; Kose, M. E.; Rupert, B. L.; Ginley, D. S.; Rumbles, G.; Shaheen, S. E.; Kopidakis, N. Structure-Dependent Photophysics of First-Generation Phenyl-Cored Thiophene Dendrimers. Chem. Mater. 2009, 21, 287-297.
121. Köse, M. E.; Mitchell, W. J.; Kopadakis, N.; Chang, C. H.; Shaheen, S. E.; Kim, K.; Rumbles, G. Theoretical Studies on Conjugated Phenyl-Cored Thiophene Dendrimers for Photovoltaic Applications. J. Am. Chem. Soc. 2007, 127, 14257-14270.
122. Kopidakis, N.; Mitchell, W. J.; Van de Lagemaat, J.; Ginley, D. S.; Rumbles, G.; Shaheen, S. E. Bulk heterojunction organic photovoltaic devices based on phenyl-cored thiophene dendrimers. Appl. Phys. Lett. 2006, 89, 103524-103526.
123. Nakao, K.; Nishimura, M.; Tamachi, T.; Kuwatani, Y.; Miyasaka, H.; Nishinaga, T.; Iyoda, M. Giant Macrocycles Composed of Thiophene, Acetylene, and Ethylene Building Blocks. J. Am. Chem. Soc. 2006, 128, 16740-16747.
124. Huang, X.; Zhu, C.; Zhang, S.; Li, W.; Guo, Y.; Zhan, X.; Liu, Y.; Bo, Z. Porphyrin-Dithienothiophene Π-Conjugated Copolymers: Synthesis and Their Applications in Field-Effect Transistors and Solar Cells. Macromolecules 2008, 41, 6895-6902.
125. Suzuki, A.; Miyaura, N. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem. Rev. 1995, 95, 2457-2483.
126. Saito, S.; Ohtani, S.; Miyaura, N. Synthesis of Biaryls via a Nickel(0)- Catalyzed Cross-Coupling Reaction of Chloroarenes with Arylboronic Acids. J. Org. Chem. 1997, 62, 8024-8030.
127. Chemler, S. R.; Trauner, D.; Danishefsky S. J. The B-Alkyl Suzuki-Miyaura Cross-Coupling Reaction: Development, Mechanistic Study, and Applications in Natural Product Synthesis A list of abbreviations can be found at the end of the article. Angew. Chem. Int. Ed. 2001, 40, 4544-4568.
128. Miyaura, N.; Yanagi, T.; Suzuki, A. The palladium-catalyzed cross-coupling reaction of phenylboronic acid with haloarenes in the presence of bases. Synth. Commun. 1981, 11, 513-519
129. Suzuki, A. Organoboron compounds in new synthetic reactions. Pure Appl. Chem. 1985, 57, 1749-1758.
130. Miyaura, N.; Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem. Rev. 1995, 95, 2457-2483.
131. Miyaura, N. Advances in Metal-organic Chemistry; Libeskind, L. S., Ed.; Jai: London, 1998; Vol. 6, pp 187-243.
132. Nolan, S. P., Ed. Suzuki-Miyaura, α-Ketone Arylation and Dehalogenation Reactions Catalyzed by a Versatile N-Heterocyclic Carbene-Palladacycle Complex. N-Heterocyclic Carbenes in Synthesis; Wiley-VCH: New York, 2006.
133. Glorius, F., Ed. N-Heterocyclic Carbenes in Transition Metal Catalysis; Topics in Organometallic Chemistry, Vol. 21; Springer-Verlag: Berlin/ Heidelberg, Germany, 2007.
134. Martin, R.; Buchwald, S. L. Palladium-Catalyzed Suzuki-Miyaura Cross- Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands. Acc. Chem. Res. 2008, 41, 1461-1473.
135. Li, W.; Han, Y.; Li, B.; Liu, C.; Bo, Z. Tris[tri(2- thienyl)phosphine]palladium as the catalyst precursor for thiophene-based Suzuki-Miyaura crosscoupling and polycondensation. J J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 4556-4563.
136. Liversedge, I. A.; Higgins, S. J.; Giles, M.; Heeneyb, M.; McCulloch, I. Suzuki route to regioregular polyalkylthiophenes using Ir-catalysed borylation to make the monomer, and Pd complexes of bulky phosphanes as coupling catalysts for polymerisation. Tetrahedron Lett. 2006, 47, 5143-5146.
137. Zhu, Y.; Champion, R. D.; Jenekhe, S. A. Conjugated Donor-Acceptor Copolymer Semiconductors with Large Intramolecular Charge Transfer: Synthesis, Optical Properties, Electrochemistry, and Field Effect Carrier Mobility of Thienopyrazine-Based Copolymers. Macromolecules 2006, 39, 8712-8719.
138. Jung, I. H.; Jung, Y. K; Lee J.; Park J.-H.; Woo H. Y.; Lee J.-I.; Chu, H. Y.; Shim, H.-K. Synthesis and Electroluminescent Properties of Fluorene-Based Copolymers Containing Electron-Withdrawing Thiazole Derivatives. J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 7148-7161.
139. Tang, W.; Kietzke, T.; Vemulamada, P.; Chen, Z.-K. Synthesis, characterization, and photovoltaic properties of novel conjugated copolymers derived from phenothiazines. J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 5266-5276.
140. Cherioux, F.; Maillotte, H.; Audeberta, P.; Zyss, J. Synthesis and characterization of an octupolar polymer and new molecular octupoles with offresonant third order optical nonlinearities. Chem. Commun. 1999, 20, 2083-2084.
141. Yamamoto, T.; Watanabe, S.; Fukumoto, H.; Sato, M.; Tanaka, T. New Heteroaromatic Polymers Consisting of Alkyl- and Amino-1,3,5-triazine Units. Their Basic Optical Properties and n-Type Time-of-Flight Drift Mobility. Macromol. Rapid Commun. 2006, 27, 317-321.
142. Zou, L.; Fu, Y.; Yan, X.; Chen, X.; Qin, J. Linear Π-conjugated polymers containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit: Synthesis and optical properties. J. Polym. Sci. Part A: Polym. Chem. 2007, 46, 702-712.
143. Yamamoto, T.; Ootsuka, H.; Iijima, T. A New Π-Conjugated Polymer Containing Isothianaphthene and Dialkoxy-p-phenylene Units: Self-Assembly and Electronic and Optical Properties. Macromol. Rapid. Commun. 2007, 28, 1786-1791.
144. Jung, Y.-K.; Kim, H.; Park, J.-H.; Lee, J.; Lee, S.K.; Lee, Y. S.; Shim, H.-K. Alternating fluorene copolymers containing isothianaphthene derivatives: A study of their aggregation properties and small band gap. J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 3573-3590.
145. Jenekhe, S. A. A class of narrow-band-gap semiconducting polymers. Nature 1986, 322, 345-347.
146. Zhang, M.; Tsao, H. N.; Pisula, W.; Yang, C.; Mishra, A. K.; Müllen, K. Field-Effect Transistors Based on a Benzothiadiazole-Cyclopentadithiophene Copolymer. J. Am. Chem. Soc. 2007, 129, 3472-3473.
147. Mühlbacher, D.; Scharber, M.; Morana, M.; Zhu, Z.; Waller, D.; Gaudiana, R.; Brabec, C. High photovoltaic performance of a low-bandgap polymer. Adv. Mater. 2006, 18, 2884-2889.
148. Xiao, S.; Zhou, H.; You, W. Conjugated Polymers of Fused Bithiophenes with Enhanced Π-Electron Delocalization for Photovoltaic Applications. Macromolecules 2008, 41, 5688-5696.
149. Zhang, F. L.; Jespersen, K. G.; Bjorstrom, C.; Svensson, M.; Andersson, M. R.; Sundstrom, V.; Magnusson, K.; Moons, E.; Yartsev, A.; Inganas, O. Influence of solvent mixing on the morphology and performance of solar cells based on polyfluorene copolymer/fullerene blends. Adv. Funct. Mater. 2006, 16, 667-674.
150. Baumgartner, T.; Bergmans, W.; Kárpati, T.; Neumann, T.; Nieger, M.; Nyuláski, L. From model compounds to extended Π-conjugated systems: Synthesis and properties of dithieno[3,2-b:2'3'-d]phospholes. Chem. Eur. J. 2005, 11, 4687-4699.
151. Baumgartner, T.; Wilk, W. Synthesis and Unexpected Reactivity of Si-H Functionalized Dithieno[3,2-b:2',3'-d]phospholes. Org. Lett. 2006, 8, 503-506.
152. Durben, S.; Dienes, Y.; Baumgartner, T. Cationic dithieno[3,2-b:2',3'- d]phospholes: A new building block for luminescent, conjugated polyelectrolytes. Org. Lett. 2006, 8, 5893-5896.
153. Hobbs, M. G.; Baumgartner, T. Recent developments in phospholecontaining oligo- and polythiophene materials. Eur. J. Inorg. Chem. 2007, 23, 3611-3628.
154. Wang, F.; Luo, J.; Yang, K.; Chen, J.; Huang, F.; Cao, Y. Conjugated Fluorene and Silole Copolymers: Synthesis, Characterization, Electronic Transition, Light Emission, Photovoltaic Cell, and Field Effect Hole Mobility. Macromolecules 2005, 38, 2253-2260.
155. Cheng, F.; Imin, P.; Maunders, C.; Botton, G.; Adronov, A. Soluble, discrete supramolecular complexes of single-walled carbon nanotubes with fluorine based conjugated polymers. Macromolecules 2008, 41, 2304-2308.
156. Chen, X.; Gholamkhass, B.; Han, X.; Vamvounis, G.; Holdcroft, S. Polythiophene- graft-styrene and polythiophene-graft-(styrene-graft-C 60) copolymers. Macrom. Rapid Commun. 2007, 28, 1792-1797.
157. Wu, S.-H.; Huang H.-M.; Chen, K.-C.; Hu, C.-W.; Hsu, C.-C.; Tsiang, R.C.- C. A green polymeric light-emitting diode material: Poly(9,9- dioctylfluorene- alt-thiophene) end-capped with gold nanoparticles. Adv. Funct. Mater. 2006, 16, 1959-1966.