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

由芳香族结构单元组成的聚合物由于主链的pi共轭结构而表现出导电性、光致发光和非线性光学行为。它们基本上分为两类：一类是富电子芳环的聚合物，如聚噻吩环和多硒环，掺杂氧化剂得到导电材料；另一类是含有缺电子芳香环的聚合物，如聚吡啶和聚喹恶啉，它们经过化学和电化学的n掺杂。本研究的目的是合成和表征交替含有富电子和贫电子芳环的新型聚酰亚胺共轭聚合物，并将其应用于电化学和光学材料。镍(0)络合物促进二溴(吡啶并噻吩基)的脱卤化缩聚反应，得到主链上含有交替的噻吩环和吡啶环的聚合物。各种聚酰亚胺共轭聚合物…类似地，从二卤代芳香族化合物中得到了更多同时含有富电子和贫电子芳环的Er。引入几个有机基团作为聚合物的侧链，有助于提高聚合物的溶解度或调节聚合物的电子态。聚(吡啶)噻吩具有独特的电化学行为，表现出氧化和还原电位的差异，这比一般可逆氧化还原的预期要大得多。这归因于观察到分子中的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很低的电势下经历还原的新的电子态。该聚合物的三阶非线性光学性能优于聚(噻吩基)和聚吡啶(聚(吡啶))，这是由于在聚合物链中含有噻吩环和吡啶环的连接处。综上所述，我成功地制备了交替含有富电子和贫电子芳环的新型聚酰亚胺共轭聚合物，并发现了独特的电化学性质和光学性质。较少

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