Long-Range Inorganic Electron Transfer: Tunneling through Covalent Bridges and Solvents

化学系的无机、生物无机和有机金属化学项目支持加州理工学院Harry B. Gray和Jay R. Winkler教授的研究。该项目旨在探索远距离电子转移和电子在蛋白质等材料中隧穿的作用。这种类型的电子转移对桥和供体和受体之间的能量差极为敏感。在氧化还原位的电势与桥位的电势相差不大的系统中，当电子在超过20埃的距离上转移时，隧道能量效应应该很容易观察到。聚氧乙烯桥联双核材料是专门为满足这些标准而设计的。距离衰减参数将从电子转移速率与桥中二甲苯单元数的相关性中提取。电子转移反应是最简单的化学转化，因为电子从供体转移到受体时不会形成或破坏化学键。当氧化还原伙伴被长距离分离时，电子转移的速率由中间介质介导。本研究将研究电桥中电子态与供体和受体金属离子电子态之间能量差的影响。

The Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division is supporting the research of Professors Harry B. Gray and Jay R. Winkler, California Institute of Technology. This project aims to probe long-range electron transfer and the role of electron tunneling through materials such as proteins. Electron transfer of this type is extremely sensitive to the difference in energy between the bridge and those of the donor and acceptor. Tunneling-energy effects should be readily observable for electron transfer over distances greater than twenty Angstroms in systems where the potentials of the redox sites differ only marginally from those of the bridge sites. Oligoxylyene-bridged binuclear have been designed specifically to meet these criteria. Distance decay parameters will be extracted from correlations of electron transfer rates to the number of xylene units in the bridge.Electron-transfer reactions are the simplest of chemical transformations in that no bonds are formed or broken as the electron migrates from the donor to the acceptor. When the redox partners are separated by long distances, the rate of electron transfer is mediated by the intervening medium. This research will study the effects of energy differences between electronic states in the bridge and those of the donor and acceptor metal ions.