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

1.蒽烯激发态的偶极矩用大坂大学的时间分辨吸收光谱和发射光谱以及美因茨大学的积分电光发射测量研究了蒽烯（两个、三个和四个蒽在9位上通过单键相连）激发态的溶剂诱导电子结构变化。发现2，3-二己基取代的三蒽烯和四蒽烯在极性溶剂中的电子结构与联蒽基的情况类似，是离子型的，而2，6-二叔丁基取代的二蒽烯、三蒽烯和四蒽烯在极性溶剂中的电子结构也显示出激子性质.这些化合物在溶液中激发态的动力学行为可以用大振幅运动与溶剂取向涨落耦合的势能面交叉来理解。2.对氨基苯硫基在光致变色作用下的孪晶复合和二聚体形成 ...更多信息 氨基苯二硫醚的缔合通过皮秒瞬态吸收光谱测量将对氨基苯硫基的成对自由基、自由基和偶极二聚体自由基彼此区分开。可以追踪三种组分的动力学行为，从中提取微观区域内反应物的双分子反应和扩散过程的信息。双生自由基复合的直接测量为研究键断裂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。3.卟啉连接富勒烯中的光诱导电子转移首次观察到四苯基锌卟啉单重激发态到富勒烯C_2上的分子内电子转移<60>。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，受激卟啉向C_2的能量转移<60>与电子转移存在一定程度的竞争。结果表明，C_2<60>是一种很有前途的人工光合作用构件。少

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