The Chemistry of the Multielectron Excited State

这个无机、生物无机和有机金属化学项目的奖项支持密歇根州立大学化学系的Daniel G. Nocera对多电子氧化还原过程的研究。长期目标是详细了解多电子过程的机理，以便合理设计原子转移和还原消除等反应。研究四重键金属-金属配合物的金属局域激发态反应。钨钼配合物和混合价双核氟膦铑配合物将被合成用于研究。产生的光激发中间体将通过皮秒和纳秒时间分辨激发态光谱进行表征。太阳能光电转换作为一种促进需要多个电子运动的复杂化学转化的有效手段，具有巨大的潜力。这样的反应发生在自然系统的固氮过程中，但化学家们还没有充分了解反应的细节，以便能够设计出有利于利用阳光而不是热量的反应。许多已知的过程都涉及单电子过程。该项目将提供有关断键和成键反应的额外信息，这是化学转化的基础，通常涉及多个电子。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on multielectron oxidation-reduction processes by Daniel G. Nocera of the Chemistry Department, Michigan State University. The long-term goal is to develop detailed understanding of the mechanism of multielectron processes in order to enable rational design of reactions such as atom transfer and reductive elimination. Reactions of metal-localized excited states of quadruply bonded metal-metal complexes will be investigated. Tungsten and molybdenum complexes and mixed-valence binuclear rhodium fluorophosphine complexes will be synthesized for use in the studies. The photoexcited intermediates generated will be characterized by picosecond and nanosecond time-resolved excited state spectroscopy. Solar photoconversion has great potential as an efficient means of promoting complex chemical transformations which require movement of more than one electron. Such reactions occur in natural systems during nitrogen fixation, but chemists have yet to understand the reaction details well enough to be able to design reactions in which sunlight rather than heat is used beneficially. Much of what is known involves one-electron processes. This project will provide additional information on reactions involving bond breaking and bond making, which are fundamental to chemical transformations and generally involve multiple electrons.