Bond Coupled Electron Transfer Reactions

罗切斯特大学化学系的乔舒亚·古德曼教授在有机动力学项目的支持下，探索了电子转移反应不同方面的详细机理研究。这项研究的核心概念是，将电子转移过程耦合到键断裂和成键事件可以提高电子转移反应的效率。该研究计划专门针对返回电子转移(RET)和解离返回电子转移(DRET)之间的竞争。前者是一种浪费能量的衰变过程，在单重态和三重态自由基离子对中都得到了广泛的研究。后者是一个相当专业的过程，仅在有限底物的高度限制条件下对三重态自由基离子对发生。扩展DRET过程的范围将引起光致电子转移领域的专家的兴趣。键耦合电子转移(BCET)反应具有驱动化学反应的潜力。这个项目试图调查这些反应中的几个。古德曼教授将主要关注DRET反应，这些反应涉及(1)二取代环丙烷和二芳基乙烷中的C-C键，(2)二硅烷中的硅-硅键，以及(3)取代的苄基卤化物中的C-卤键。对光诱导电子转移反应中的RET过程的更好的理解可能最终导致利用光驱动化学反应的能力。例如，有一天可能会在成像应用中使用由光诱导的聚合。拟议中的二硅烷研究可能会对光刻抗蚀剂、非线性光学材料和一维导体的发展产生影响。

Professor Joshua Goodman of the Department of Chemistry at the University of Rochester, with the support of the Organic Dynamics Program, explores detailed mechanistic studies on different aspects of electron transfer reactions. The proposed research is centered on the concept that coupling the electron transfer processes to bond breaking and bond making events can increase the efficiency of electron transfer reactions. The research plan deals exclusively with the competition between return electron transfer (RET) and dissociative return electron transfer (DRET). The former is an energy-wasting decay process that has been widely studied in both singlet and triplet radical ion pairs. The latter is a rather specialized process that occurs only for triplet radical ion pairs under highly restrictive conditions for a limited set of substrates. Extensions of the scope of the DRET process will be of interest to specialists in the field of photoinduced electron transfer.Bond coupled electron transfer (BCET) reactions have the potential to drive chemical reactions. This project seeks to investigate several of these reactions. Professor Goodman will focus primarily on DRET reactions that involve cleavage of (1) C-C bonds in disubstituted cyclopropanes and diarylethanes, (2) Si-Si bonds in disilanes, and (3) C-halogen bonds in substituted benzylic halides. An improved understanding of RET processes in photoinduced electron transfer reactions may eventually lead to the ability to drive chemical reactions using light. For example, it may be possible one day to employ polymerizations induced by light in imaging applications. The proposed investigation on disilanes may have an impact on developing lithographic resists, nonlinear optical materials, and one-dimensional conductors.