Picosecond 'Cage Effects' in Coordination Compounds

本研究拟在化学系进行 在加州大学圣地亚哥分校， 时间分辨激光光谱学来探测 刘易斯酸碱反应溶剂笼效应 的 酸碱对将通过光解解离产生， 来自六配位铁卟啉络合物的配体。 温度和/或压力的变化将用于延长 光谱实验的时间范围， 有助于确定反应的哪一部分发生 在溶剂笼中，以及在溶剂笼扩散后发生了什么。 从溶剂笼中取出试剂。 %%% 麻省理工学院化学系的道格拉斯马格德教授 加州大学圣地亚哥分校将对 反应物分子对产生在紧密接近， 溶液 这些分子的后续反应将是 使用快速光谱方法进行监测， 周围的溶剂分子是否提供笼效应 用来将反应物固定在一起，或者 分子完全可以自由地分开， 后来的遭遇。 这些研究旨在提供 对所有反应都很重要的基本信息 在溶液中。 选择用于研究的反应物与 生物氧载体，使结果将有 特别适用于生物功能。

This research, to be conducted in the Department of Chemistry at the University of California, San Diego, will utilize time-resolved laser spectroscopy to probe for evidence of solvent cage effects on Lewis acid base reactions. The acid-base pair will be generated by photolytic dissociation of a ligand from a six-coordinate, iron-porphyrin complex. Changes in temperature and/or pressure will be used to extend the temporal range of the spectroscopic experiments, which will be helpful in determining what portion of the reaction occurs in the solvent cage and what occurs after diffusion of the reagents out of the solvent cage. %%% Professor Douglas Magde of the Department of Chemistry at the University of California, San Diego will conduct experiments on pairs of reactant molecules generated in close proximity in solution. Subsequent reactions of these molecules will be monitored using rapid spectroscopic methods to determine whether the surrounding solvent molecules provide a cage effect that serves to hold the reactants together, or whether the molecules are totally free to move apart and react later in a subsequent encounter. These studies are designed to provide fundamental information important for all reactions that occur in solution. The reactants chosen for study are related to biological oxygen carriers so that the results will have special applicability to biological functions.