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

化学部的无机化学、生物无机化学和金属有机化学计划正在支持加州理工学院教授哈里·B·格雷和杰伊·R·温克勒的研究。该项目旨在探索远程电子转移以及电子通过蛋白质等材料的隧穿作用。这种类型的电子转移对桥与施主和受主之间的能量差非常敏感。在氧化还原位的电位与桥位的电位仅有微小差异的系统中，对于超过20埃的电子转移，隧道能量效应应该是容易观察到的。低聚氧基苯桥联双核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量的关系中提取。电子转移反应是最简单的化学转换，因为当电子从给体迁移到接受体时不会形成或断裂键。当氧化还原配对相隔很远的距离时，电子转移的速率由中间介质来调节。这项研究将研究桥中电子态与施主和受主金属离子的电子态之间的能量差异的影响。

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.