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Microscopic Dynamics in Solution-Solute-Solvent Interaction and Solvent-Induced Electronic Structure Cange in the Excited State

溶液-溶质-溶剂相互作用的微观动力学和激发态下溶剂诱导的电子结构变化

基本信息

批准号：
05044055
负责人：
OKADA Tadashi
金额：
$ 2.56万
依托单位：
OSAKA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

1.Dipole moment of the excited state of anthrylenesSolvent induced electronic structure change in the excited state of anthrylenes, two, three and four anthracenes are connected with each other at 9 position by a single bond, has been studied by means of time resolved absorption and emission spectroscopy at Osaka University and integral electro optical emission measurements at Mainz University. The electronic structure of 2,3-dihexyl substituted tri-and tetra-anthrylenes in polar solvents is found to be rather ionic which is similar to the case of bianthryl, while that of 2,6-di-tert-butyl substituted bi-, tri-and tetra-anthrylenes shows excitonic character even in polar solvents. The dynamical behaviors in the excited state of these compounds in solution may be understood in terms of the potential surface crossing of the large amplitude motions coupled with solvent orientational fluctuations.2.Geminate recombination and the dimer formation of p-aminophenylthiyl produced by the photodi … More ssociation of aminophenyldisulfideThe geminate pair, free radical, and dipole dimer radical of p-aminophenylthiyl are distinguished from each other by picosecond transient absorption spectral measurements. The dynamic behavior of three species can be traced, from which the information about the bimolecular reaction and the diffusion process of reactants in a microscopic region can be extracted. The direct measurements of geminate radical recombination provide fundamental information on the solvent cage effect in bond cleavage reaction, as well as on the dynamical behaviors of the collision pair in bimolecular chemical reactions.3.Photoinduced electron transfer in porphyrin-linked fullereneIntramolecular electron transfer from the singlet excited state of zinctetraphenylporphyrin moiety to the C_<60> moiety was observed for the first time. In polar solvents such as tetrahydrofuran and dimethylformamide, the quantum yield of charge separated state is found to be 0.97. In nonpolar solvent, benzene, the energy transfer from excited porphyrin to C_<60> takes place a little bit competing with electron transfer. The results show that C_<60> is a promising candidate as building block in artificial photosynthesis. Less

1.利用大阪大学的时间分辨吸收发射光谱和美因茨大学的积分电光发射测量，研究了溶剂引起的蒽的激发态电子结构变化，二、三、四蒽以单键在9位相互连接。在极性溶剂中，2,3-二己基取代的三、四蒽的电子结构与bianthryl类似，具有较强的离子型，而2,6-二叔丁基取代的二、三、四蒽的电子结构即使在极性溶剂中也具有激子性。这些化合物在溶液中激发态的动力学行为可以用伴随溶剂取向波动的振幅运动的势面交叉来理解。利用皮秒瞬态吸收光谱测量，将对氨基苯基噻基的双生基对、自由基和偶极二聚基进行了区分。通过对三种物质的动力学行为进行跟踪，可以提取微观区域内双分子反应和反应物扩散过程的信息。双生自由基复合的直接测量为键裂解反应中的溶剂笼效应以及双分子化学反应中碰撞对的动力学行为提供了基础信息。在卟啉连接的富勒烯中，首次观察到从锌四苯基卟啉单线态激发态到C_<60>的分子内电子转移。在四氢呋喃和二甲基甲酰胺等极性溶剂中，电荷分离态的量子产率为0.97。在非极性溶剂苯中，受激发的卟啉向C_<60>的能量转移与电子转移有一定的竞争。结果表明，C_<60>是一种很有前途的人工光合作用基础材料。少