Regioregular poly(3-alkoxythiophene)s: Toward soluble, chiral conjugated polymers with a stable oxidized state

被引:82
作者
Koeckelberghs, G [1 ]
Vangheluwe, M [1 ]
Samyn, C [1 ]
Persoons, A [1 ]
Verbiest, T [1 ]
机构
[1] Katholieke Univ Leuven, B-3001 Louvain, Belgium
关键词
D O I
10.1021/ma050731p
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Chiral poly(3-(3,7-dimethyloetyloxy)thiophene)s were prepared using three different methodologies, rendering polymers with different degrees of regioregularity. In a first attempt, 3-alkoxythiophene was polymerized using FeCl3, resulting in a highly regioirregular poly(3-alkoxythiophene). Second, the GRIM methodology was applied, which yielded poly(3-alkoxythiophene)s with relatively high, but not perfect, degrees of regioregularity. Finally, an alternative methodology was used, which consisted of the exclusive formation and subsequent polymerization of 2-bromomagnesio-3-(3,7-dimethyloctyloxy)-5-bromothiophene) and which resulted in poly(3-alkoxythiophene)s with (almost) perfect regioregularity. The degrees of regioregularity were evaluated with H-1 NMR, UV-vis, and CD spectroscopy and cyclic voltammetry. These (regioregular) poly(3-alkoxythiophene)s show a very high lambda(max), indicating very high conjugation lengths. Moreover, the polymers could easily be oxidized and they were stable in both neutral as well as oxidized state. This stability can be correlated with the decrease in oxidation potential. The reproducibility and reversibility of the oxidation was demonstrated by UV-vis spectroscopy. Finally, the chiral properties of the polymers were investigated with circular dichroism spectroscopy. These experiments demonstrated again the difference in regioregularity of the polymers.
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页码:5554 / 5559
页数:6
相关论文
共 35 条
[1]  
[Anonymous], HDB CONDUCTING POLYM
[2]   Soluble and processable regioregular poly(3-hexylthiophene) for thin film field-effect transistor applications with high mobility [J].
Bao, Z ;
Dodabalapur, A ;
Lovinger, AJ .
APPLIED PHYSICS LETTERS, 1996, 69 (26) :4108-4110
[3]   Chirality in regioregular and soluble polythiophene: An internal probe of conformational changes induced by minute solvation variation [J].
Bidan, G ;
Guillerez, S ;
Sorokin, V .
ADVANCED MATERIALS, 1996, 8 (02) :157-&
[4]   CHIROPTICAL PROPERTIES OF REGIOREGULAR CHIRAL POLYTHIOPHENES [J].
BOUMAN, MM ;
HAVINGA, EE ;
JANSSEN, RAJ ;
MEIJER, EW .
MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 1994, 256 :439-448
[5]  
Brooks E, 1990, United States patent, Patent No. [4931569, 4,931,569]
[6]   Synthesis of the first enantiomerically pure and chiral, disubstituted 3,4-ethylenedioxythiophenes (EDOTs) and corresponding stereo- and regioregular PEDOTs [J].
Caras-Quintero, D ;
Bäuerle, P .
CHEMICAL COMMUNICATIONS, 2004, (08) :926-927
[7]   Synthesis and characterization of chiral conducting polymers based on polypyrrole [J].
Chen, F ;
Akhtar, P ;
KaneMaguire, LAP ;
Wallace, GG .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1997, 50 (09) :939-945
[8]   REGIOCONTROLLED SYNTHESIS OF POLY(3-ALKYLTHIOPHENES) MEDIATED BY RIEKE ZINC - THEIR CHARACTERIZATION AND SOLID-STATE PROPERTIES [J].
CHEN, TA ;
WU, XM ;
RIEKE, RD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (01) :233-244
[9]   POLY(3,3'-DIBUTOXY-2,2'-BITHIOPHENE) - A NEW HIGHLY CONJUGATED POLYTHIOPHENE DERIVATIVE [J].
CLOUTIER, R ;
LECLERC, M .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (17) :1194-1195
[10]   STRUCTURE PROPERTY RELATIONSHIPS IN ALKOXY-SUBSTITUTED POLYTHIOPHENES [J].
DAOUST, G ;
LECLERC, M .
MACROMOLECULES, 1991, 24 (02) :455-459