Femtochemistry of selected di-substituted benzenes
Femtochemistry of selected di-substituted benzenes
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DOI：
10.1016/j.jphotochem.2015.05.036
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发表时间：
2016-03-01
影响因子：
4.3
通讯作者：
Gilch, P.
中科院分区：
文献类型：
--
作者：
Froebel, S.;Gilch, P.
苯的邻位二取代反应为研究特定环境中不同官能团之间的相互作用提供了机会。取代基被强迫到允许发生化学反应的距离。在这篇专题文章中，我们重点介绍了含有硝基和羰基的光反应化合物。这些分子的复杂电子结构导致了飞秒和皮秒时间尺度上丰富的光化学。飞秒光谱技术和量子化学计算的结合表明，所有研究的化合物都通过单重态和三重态通道进行氢转移。在一些情况下，这些转移是进一步重新安排的起点。这些实验使我们能够阐明突出的光反应机理，如邻硝基苯甲醛或硝基苯衍生的耐光保护基团的光反应。(C)由爱思唯尔出版的2015年。
Ortho-di-substitution of benzenes provides the opportunity to study interactions between diverse functional groups in a defined environment. The substituents are forced to distances which allow chemical reactions to occur. In this feature article, we focus on photoreactive compounds containing nitro and carbonyl groups. The complex electronic structure of these molecules results in a rich photochemistry on the femto- and picosecond timescale. A combination of femtosecond spectroscopic techniques and quantum chemical calculations shows that all compounds studied undergo hydrogen transfers via both, singlet and triplet channels. In several cases these transfers are the starting point for further rearrangements. The experiments enabled us to elucidate the mechanisms of prominent photoreactions as the ones of ortho-nitrobenzaldehyde or of nitrobenzene derived photolabile protecting groups. (C) 2015 Published by Elsevier B.V.