Mixed-Metal Supramolecular Complexes as Photochemical Molecular Devices for Photoinitiated Electron Collection

无机、生物无机和有机金属项目的这一奖项支持弗吉尼亚理工学院化学系的凯伦·J·布鲁尔博士对光引发的电子转移反应的研究。将合成通过多吡啶桥联配体将两个光吸收金属中心共价偶联到中心金属部分的三金属络合物。在这些络合物中，配体上的低位空位轨道能够接受电子并调节金属位置之间的电子转移。为了找到促进电子聚集的最佳条件，以及了解多电子转移的细节，将对这些配合物的光物理和电化学性质进行研究。自然界中的许多重要反应，如二氧化碳的减少和固氮，都需要许多电子。这个项目的目标是研究一种促进多电子转移反应的方法。每个都能提供电子的金属络合物将以大分子的形式连接在一起。光将被用来在金属中心之间驱动电子，从而使许多电子可以进行反应。尽管这项研究只涉及这一过程的一部分，但预计将提供与开发可用于促进各种化学反应的太阳能设备有关的基本信息。

This award in the Inorganic, Bioinorganic, and Organometallic Program supports research on photoinitiated electron transfer reactions by Dr. Karen J. Brewer of the Chemistry Department, Virginia Polytechnic Institute. Trimetallic complexes which covalently couple two light-absorbing metal centers to a central metal section through polypyridyl bridging ligands will be synthesized. In these complexes, low lying unoccupied orbitals on the ligand are capable of accepting electrons and mediating the electron transfer between metal sites. The photophysical and electrochemical properties of these complexes will be studied in order to find the optimal conditions for promoting electron build-up, as well as to understand the details of multi-electron transfer. Many important reactions in nature, such as the reduction of carbon dioxide and nitrogen fixation, require many electrons. The goal of this project is to investigate a method for promoting multi-electron transfer reactions. Metal complexes which can each contribute electrons will be linked together in large molecules. Light will be used to drive electrons between metal centers so that a number of electrons can be available for reaction. Although it is concerned with only a part of the process, this study is expected to provide basic information related to the development of solar-powered devices which could be used to promote a variety of chemical reactions.