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Synthesis and Photo Electronic Properties of Novel π-Stacked Polymers

新型π堆叠聚合物的合成及光电性能

基本信息

批准号：
16550110
负责人：
NAKANO Tamaki
金额：
$ 2.37万
依托单位：
Nara Institute of Science and Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550110/
关键词：
conductive polymers π-electronic materials oxidation electron spin resonance spectrum near infra red absorption spectrum charge transfer radical cation olieomers

项目摘要

We found that free-radical polymerization under appropriate conditions can give polydibenzofulvene having a π-stacked conformation as well as anionic polymerization. The free-radical polymerization product contained a small amount of defective conformation incorporated in the chain. Such a partial conformational defect was revealed to contribute to increase solubility of the polymer. In addition, as a new bulky dibenzofulvene derivative, 2,7-di-t-butyldibenzofulvene, was synthesized and polymerized in order to examine the effect of the side chain on polymerizability of the monomer and properties of the polymerization product. The bulky new monomer showed relatively low reactivity in anionic polymerization and led to oligomers mainly up to trimer. Photophysical properties of the obtained oligomers shed light on how unsubstituted polydibenzofulvene shows hypochromicity in absorption spectra and excimer emission in fluorescence spectra. Furthermore, absorption spectra of a radical cation species of oligo- and polydibenzofulvene generated by their chemical oxidation were measured in order to obtain information on charge transport properties. The radical cation species indicated a clear charge transfer band in near IR region, supporting the proposed charge transport through the stacked fluorene rings. In addition to the above investigations on polydibenzofulvene, poly(9-fluorenyl methacrylate) having various tacticity was synthesized by stereospecific anionic polymerization technique and the structure and the properties of the polymers were examined. The aim of this investigation was to find a new π-stacked polymer having a polymethacrylate backbone. Although the polymers were found not to have a stable π-stacked conformation in solution, they showed different photophysical properties depending on the main-chain tacticity.

我们发现，在适当的条件下，自由基聚合可以得到具有π-堆积构象的聚二苯并富烯以及阴离子聚合。自由基聚合产物含有少量的缺陷构象纳入链中。这种部分构象缺陷被揭示有助于增加聚合物的溶解度。此外，本文还合成了一种新型的大体积二苯并富烯衍生物2，7-二叔丁基二苯并富烯，并对其进行了聚合，考察了侧链对单体聚合性和聚合产物性能的影响。这种体积庞大的新单体在阴离子聚合中表现出相对较低的反应活性，并导致低聚物主要为三聚体。所得低聚物的光物理性质揭示了未取代的聚二苯并富烯如何在吸收光谱中显示出减色性和在荧光光谱中显示出激基缔合物发射。此外，一个自由基阳离子物种的低聚和聚二苯并富烯的化学氧化产生的吸收光谱进行了测量，以获得有关电荷传输性能的信息。自由基阳离子物种表明在近红外区域的一个明确的电荷转移带，支持建议的电荷传输通过堆叠的芴环。在对聚二苯并富烯进行上述研究的基础上，利用阴离子聚合技术合成了具有不同立构规整度的聚甲基丙烯酸9-芴酯，并对聚合物的结构和性能进行了研究。本研究的目的是寻找一种新的具有聚甲基丙烯酸酯主链的π-堆叠聚合物。虽然聚合物在溶液中不具有稳定的π-堆积构象，但它们显示出不同的物理性质，这取决于主链的立构规整度。