Matthew J. Goodwin, John C. Dickenson, Alexia Ripak, Alexander M. Deetz, Jackson S. McCarthy, Gerald J. Meyer and Ludovic Troian-Gautier,
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引用次数: 0
摘要
利用可见光介导流体溶液中的化学反应,其应用范围从太阳能燃料生产到医药和有机合成。这些反应通常由光激发染料分子(光敏剂)和具有氧化还原作用的淬灭剂之间的电子转移引发,从而产生在溶剂笼中紧密结合的自由基对。其中许多自由基会发生热力学上有利的快速 "同位 "重组,不会扩散出包围它们的溶剂笼。那些逃出溶剂笼的自由基是有用的试剂,它们可能会发生对上述应用非常重要的后续反应。尽管数十年来人们一直在研究逸出溶剂笼的过程和决定产量的因素,但对它们的实际意义和基本重要性仍然知之甚少。本文回顾了自 J. P. Lorand 于 1972 年发表题为 "笼效应 "的开创性综述以来,有关光诱导电子转移和笼逃逸的最新研究成果。本综述还为该领域的新手提供了一些背景知识,并讨论了同解键光解离和双分子光诱导电子转移反应的笼逃逸过程。综述最后提出了未来研究的一些关键目标和方向,这些目标和方向有望将这一充满活力的领域提升到更高的高度。
Factors that Impact Photochemical Cage Escape Yields
The utilization of visible light to mediate chemical reactions in fluid solutions has applications that range from solar fuel production to medicine and organic synthesis. These reactions are typically initiated by electron transfer between a photoexcited dye molecule (a photosensitizer) and a redox-active quencher to yield radical pairs that are intimately associated within a solvent cage. Many of these radicals undergo rapid thermodynamically favored “geminate” recombination and do not diffuse out of the solvent cage that surrounds them. Those that do escape the cage are useful reagents that may undergo subsequent reactions important to the above-mentioned applications. The cage escape process and the factors that determine the yields remain poorly understood despite decades of research motivated by their practical and fundamental importance. Herein, state-of-the-art research on light-induced electron transfer and cage escape that has appeared since the seminal 1972 review by J. P. Lorand entitled “The Cage Effect” is reviewed. This review also provides some background for those new to the field and discusses the cage escape process of both homolytic bond photodissociation and bimolecular light induced electron transfer reactions. The review concludes with some key goals and directions for future research that promise to elevate this very vibrant field to even greater heights.
期刊介绍:
Chemical Reviews is a highly regarded and highest-ranked journal covering the general topic of chemistry. Its mission is to provide comprehensive, authoritative, critical, and readable reviews of important recent research in organic, inorganic, physical, analytical, theoretical, and biological chemistry.
Since 1985, Chemical Reviews has also published periodic thematic issues that focus on a single theme or direction of emerging research.