Dynamics and mechanism of delocalized cationic state in organic photoconductive polymers

有机光电导聚合物中离域阳离子态的动力学和机理

• 批准号: 23245004
• 负责人: MIYASAKA Hiroshi
• 金额: $ 15.64万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011-11-18 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-23245004/
• 关键词: 光誘起電子移動; ホール移動; 有機光伝導体; フェムト秒分光; 過渡二色性; 電荷シフト反応; 非局在イオン状態; 過渡吸収二色性; 近赤外分光; 電子移動; 光電導; 有機光電導体; 非局在イオン; 光電変換; ホール電導; ホッピング電導

To elucidate factors enabling the rapid charge shift reaction in the charge-separated state produced by photoinduced charge separation in molecular assemblies, we have studied the electron transfer dynamics in aromatic vinyl polymer systems in solid phase where rapid charge shift reaction takes place among aromatic groups after the photoexcitation. By femtosecond transient absorption spectroscopy and dichroism measurements in the temperature range of 10 to 295 K, it was revealed that the delocalization process of the cationic state occurred among several aromatic groups very rapidly. This delocalization leads to the increase in the inter-ionic distance between the anion and the cation resulting in the reduction of the attractive Coulombic interaction and the increase in the cationic size reduces the reorganization energy. These factors facilitate the rapid charge shift reaction which has not been well accounted for by the conventional electron transfer theories.

为了阐明在分子组装体中光诱导电荷分离产生的电荷分离态中快速电荷转移反应的因素，我们研究了固相中芳香族乙烯基聚合物体系中的电子转移动力学，其中在光激发后芳香族基团之间发生快速电荷转移反应。通过飞秒瞬态吸收光谱和二色性测量的温度范围为10至295 K，它揭示了阳离子态的离域过程中发生的几个芳香基团非常迅速。这种离域导致阴离子和阳离子之间的离子间距离的增加，导致吸引库仑相互作用的减少，并且阳离子尺寸的增加降低了重组能。这些因素促进了快速的电荷转移反应，而传统的电子转移理论并没有很好地解释这种反应。

项目成果

芳香族高分子系の電子移動反応

芳香族聚合物体系中的电子转移反应

Metallic-Nanostructure-Enhanced Optical Trapping of Flexible Polymer Chains in Aqueous Solution As Revealed by Confocal Fluorescence Microspectroscopy

• DOI: 10.1021/jp305247a
• 发表时间: 2012-06
• 期刊: Journal of Physical Chemistry C
• 影响因子: 3.7
• 作者: Mariko Toshimitsu;Yuriko Matsumura;T. Shoji;N. Kitamura;Mai Takase;K. Murakoshi;H. Yamauchi;S. Ito;H. Miyasaka;A. Nobuhiro;Y. Mizumoto;H. Ishihara;Yasuyuki Tsuboi

Ultrafast Delocalization Dynamics of Cationic States in Photoconductive Poly(N-vinylcarbazole) Amorphous Solid

光电导聚（N-乙烯基咔唑）非晶固体中阳离子态的超快离域动力学

• 发表时间: 2012
• 作者: 一瀬麻沙美;安富陽一;末松英浩;西岡洋太;内田竜也;香月勗;Hiroshi Miyasaka
• 通讯作者: Hiroshi Miyasaka

光誘起電子移動,"発光の辞典", 太田信廣ら編

光诱导电子转移，《发光词典》，太田信弘等人编辑。

• 作者: 宮坂 博;片山哲郎
• 通讯作者: 片山哲郎

Temperature near Gold Nanoparticles under Photoexcitation: Evaluation Using a Fluorescence Correlation Technique

光激发下金纳米粒子附近的温度：使用荧光相关技术进行评估

• 发表时间: 2013
• 期刊: J. Phys. Chem. C
• 影响因子: 3.7
• 作者: H. Yamauchi;S. Ito; K. Yoshida;T. Itoh;Y. Tsuboi;N. Kitamura;H Miyasaka
• 通讯作者: H Miyasaka