Homogeneous and Heterogeneous Electron-Transfer Reactions

该项目属于分析和表面化学的一般领域，以及金属有机电化学的子领域。在这项为期三年的持续资助期间，盖革教授和他的学生将继续进行单电子和双电子转移反应的基础研究，这些反应旨在阐明这些具有重要技术意义的化学体系的机械方面。电化学和光谱技术将与包含多个金属氧化还原中心的精心设计的分子骨架相结合，以测试跨空间电子离域、相邻氧化还原中心的协同反应以及弱耦合氧化还原中心之间的远距离相互作用。此外，还将开发一种合理的实验方法来比较均匀电子转移过程与其非均相类似物的距离相关性。这项研究建立在盖革博士之前的美国国家科学基金会拨款CHE-8603728下所取得的成果的基础上，旨在为导电材料以及光合作用和其他生物电子转移反应的基本方面提供基本的见解。此外，这些研究对于进一步了解作为工业重要催化系统的混价化合物的行为是重要的。

This project is in the general area of analytical and surface chemistry and in the subfield of organometallic electrochemistry. During the tenure of this three-year continuing grant, Professor Geiger and his students will pursue fundamental investigations of one-electron and two-electron transfer reactions that are designed to elucidate mechanistic aspects of these technologically important types of chemical systems. Electrochemical and spectroscopic techniques will be used in conjunction with well designed molecular frameworks containing multiple metal redox centers to test through-space electron delocalization, the cooperative reactivity of adjacent redox centers, and long distance interactions between weakly coupled redox centers. Also, a sound experimental approach will be developed for comparing the distance dependence of homogeneous electron transfer processes with their heterogeneous analogues. %%% This research builds upon results obtained under Dr. Geiger's previous NSF grant, CHE-8603728, to provide basic insights into fundamental aspects of conducting materials and of photosynthetic and other biological electron transfer reactions. Additionally, these studies are important to further understanding the behavior of mixed-valent compounds that function as industrially important catalytic systems.