Picosecond 'Cage Effects' in Coordination Compounds

这项研究将在加州大学圣地亚哥分校化学系进行，将利用时间分辨激光光谱学来探索溶剂笼对Lewis酸碱反应影响的证据。酸碱对将由六配位的铁-卟啉络合物的配体光解解离而产生。温度和/或压力的变化将被用来扩大光谱实验的时间范围，这将有助于确定反应的哪一部分发生在溶剂笼中，以及试剂扩散出溶剂笼后发生了什么。加州大学圣地亚哥分校化学系的道格拉斯·马格德教授将对溶液中近距离产生的反应物分子对进行实验。这些分子的后续反应将使用快速光谱方法进行监测，以确定周围的溶剂分子是否提供了将反应物保持在一起的笼子效应，或者分子是否完全自由地移动并在随后的相遇中发生反应。这些研究旨在为溶液中发生的所有反应提供重要的基本信息。所选择的反应物与生物氧载体有关，因此结果对生物功能具有特殊的适用性。

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.