离子对内电子转移型染料阴离子-翁盐阳离子光敏体系中的溶剂效应和结构效应

本文研究了溶剂效应和结构效应对染料碘翁盐光物理, 光化学性质的影响。观察到在溶剂中离子对可以各种形式存在, 如紧密离子对、溶剂分隔离子对或溶剂化的自由离子, 溶剂的极性不仅影响各种存在形式的光谱性质, 而且影响它们之间的平衡关系, 进而影响离子对体系的物理化学性质。染料母核和碘翁阳离子的结构均对离子对体系的性质有影响。光诱导电子转移反应的热力学驱动力越大, 反应速度越快。用分子模拟技术(Molecular Modeling)对离子对体系的立体结构进行了研究, 为理解离子对体系的各种物理化学行为提供了重要的参考。

Solvent effects and structure effects in intra-ion-pair electron transfer dye anion-iodonium

Effects of solvent and structure on the photophysical and photochemical properties of dye-onium salts have been studied in this report. It is shown that in solution the ion pairs can exist in such different forms as contact ion pair, solvent-separated ion pair or free solvated ions. Solvent polarity influences not only the spectral properties of different forms, but the equilibrium between them as well, leading to change of physicochemical properties of the ion pairs. Ion pairs with different structure of either dye anion or onium cation have different properties. The greater the thermodynamic driving force, the faster the photoinduced electron transfer reaction is. The ion pair system has been modeled using the Molecular Modeling technique, providing some important information for understanding the physicochemical behaviors of the ion pair systems.