New low-gap polymers from 3,4-ethylenedioxythiophene-bis-substituted electron-poor thiophenes. The roles of thiophene, donor-acceptor alternation, and copolymerization in intrinsic conductivity

被引:123
作者
Berlin, A
Zotti, G
Zecchin, S
Schiavon, G
Vercelli, B
Zanelli, A
机构
[1] CNR, Ist Sci & Tecnol Mol, I-20133 Milan, Italy
[2] CNR, Ist Energet & Interfasi, I-35127 Padua, Italy
[3] CNR, Ist Sintesi Organ & Fotoreatt, I-40129 Bologna, Italy
关键词
D O I
10.1021/cm049572z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
New low-gap thiophene-based regular copolymers are produced by anodic coupling of 3,4-ethylenedioxythiophene-2,5-substituted thieno[3,4-b]pyrazine (TP), cyclopenta[2,1-b;3,4-b']dithiophen-4-one (CO), and 4-dicyanomethylene-4H-cyclopenta[2,1-b;3,4-b']dithiophene (CN). The copolymers are characterized by cyclic voltammetry, FTIR reflection-absorption and UV-vis spectroscopy, electrochemical quartz crystal microbalance analysis, and in situ p- and n-conductivity measurement. The copolymers show low optical gaps (measured at the maximum absorption) and electrochemical gaps (measured from redox potentials) in the range 0.8-1.3 eV. The CN-based polymer displays the lowest reported electrochemical gap (0.8 V). Random copolymers of CO and 3,4-ethylenedioxythiophene (EDT) have also been produced and compared with the relevant regular copolymer. Copolymerization of CO with increasing amounts of EDT decreases the gap. From an analysis of redox potential as a function of EDT fraction, it is found that the gap is limited by the redox potentials of the individual homopolymers. Localization of n-doping carriers in the polythiophene chains is progressively increased by donor-acceptor alternation and then by copolymerization till the expected intrinsic conductivity is made completely p-type.
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页码:3667 / 3676
页数:10
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