Benniston Andrew C, Harriman Anthony
Molecular Photonics Laboratory, School of Natural Sciences, Bedson Building, University of Newcastle, Newcastle upon Tyne, UK NE1 7RU.
Chem Soc Rev. 2006 Feb;35(2):169-79. doi: 10.1039/b503169a. Epub 2005 Nov 30.
This tutorial review illustrates the many facets whereby the molecular conformation helps to control the rates of through-bond electron transfer. A brief introduction to Marcus theory is given, highlighting the importance of the coupling element and the super-exchange mechanism, before considering the reasons why the coupling element might depend on the molecular geometry. The methods currently available for determination of both the coupling element and the geometry are reviewed and various examples are given for systems where the structure controls the degree of electronic coupling along the molecular axis. The role of the "bridge" connecting the donor and acceptor is emphasized.
本教程综述阐述了分子构象有助于控制通过化学键的电子转移速率的多个方面。在考虑耦合元件可能依赖于分子几何形状的原因之前，简要介绍了马库斯理论，强调了耦合元件和超交换机制的重要性。综述了目前可用于确定耦合元件和几何形状的方法，并给出了各种示例，说明结构如何控制沿分子轴的电子耦合程度。强调了连接供体和受体的“桥”的作用。
