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Synthesis of Novel Electrically Conductive pi-Conjugated Polymers with Charge Transferred Structure Along the Polymer Chain

沿聚合物链具有电荷转移结构的新型导电π共轭聚合物的合成

基本信息

批准号：
07455369
负责人：
YAMAMOTO Takakazu
金额：
$ 4.74万
依托单位：
TOKYO INSTITUTE OF TECHNOLOGY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Polymers composed of aromatic structural units show both electrical conductivity, photoluminescence, and non-linear optical behavior owing to the pi-conjugated structure of the main chain. They are basically classified into polymers containing electron rich aromatic rings such as polythiophene and polyselenophene that are doped with oxidant to give electrically conductive materials and those having electron deficient aromatic such as polypyridine and polyquinoxaline that undergo chemical and electrochemical n-doping. The present study aims synthesis and characterization of novel pi-conjugated polymers containing electron rich and electron poor aromatic rings in an alternating fashion as well as utilization of the resulting polymers to electrochemical and optical materials.Ni (0) complex promoted dehalogenative polycondensation of dibromro (pyridylthiophene) gave the corresponding polymer composed of alternating thiophene and pyridine rings in the main chain. Various pi-conjugated polym … More ers containing both electron rich and electron poor aromatic rings were obtained similarly from dihaloaromatic compounds. Introduction of several organic groups as the side chain of the polymers was helpful to increase the solubility or to tune the electronic state of the polymers. Poly (pyridyl) thiophene had unique electrochemical behavior and showed the difference between the oxidation and reduction potentials, which were much larger than expected for common reversible redox. It is attributed to the observation that one electronic oxidation of the thiophene ring in the molecule induce charge transfer in the structural unit to result in a novel electronic state of the structural unit that undergoes reduction at very low potential. The polymer shows the third-order non-linear optical property better than poly (thiophene) and poly (pyridine) owing to a junction of thiophene and pyridine ring in the polymer chain.In summary, I have suceeded in preparation and characterization of novel pi-conjugated polymers containing electron rich and poor aromatic rings alternatingly and found unique elctrochemical and optical properties. Less

由芳香族结构单元组成的聚合物由于主链的π共轭结构而显示出导电性、光致发光和非线性光学行为。它们基本上被分类为含有富电子芳环的聚合物，例如聚噻吩和聚硒醚，其被氧化剂掺杂以得到导电材料，以及具有缺电子芳环的聚合物，例如聚吡啶和聚喹喔啉，其经历化学和电化学n-掺杂。本研究的目的是合成和表征新型的π共轭聚合物，并将其应用于电化学和光学材料中，通过Ni（0）配合物促进二溴（吡啶基噻吩）的脱卤缩聚反应，得到相应的主链上噻吩环和吡啶环交替排列的聚合物。各种π共轭聚合物 ...更多信息类似地从二卤代芳族化合物获得含有富电子和贫电子芳族环的ERS。在聚合物侧链中引入多个有机基团有助于提高聚合物的溶解性或调节聚合物的电子状态。聚吡啶噻吩具有独特的电化学行为，其氧化还原电位差比一般可逆氧化还原电位差大得多。这归因于观察到分子中噻吩环的一个电子氧化诱导结构单元中的电荷转移，从而导致结构单元在非常低的电势下经历还原的新电子状态。由于聚合物链中噻吩环和吡啶环的连接，使聚合物显示出比聚噻吩和聚吡啶更好的三阶非线性光学性能。综上所述，本论文成功地制备和表征了新型的含富电子和贫电子芳香环的π共轭聚合物，发现了其独特的电化学和光学性质。少