Tuning Excited-State Reactivity by Proton-Coupled Electron Transfer

被引：17

作者：

Li, Han ^{[1
]}

Zhang, Ming-Tian ^{[1
]}

机构：

[1] Tsinghua Univ, Dept Chem, Ctr Basic Mol Sci CBMS, Beijing 100084, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 42期

基金：

中国国家自然科学基金;

关键词：

electron transfer; hydrogen-atom transfer; kinetic isotope effect; photochemistry; triplet states; ARTIFICIAL PHOTOSYNTHESIS; PHOTOINDUCED ELECTRON; CONCERTED PATHWAYS; TYROSINE OXIDATION; PHOTOSYSTEM-II; WATER; ACETONITRILE; TRYPTOPHAN; DEPENDENCE; CONSTANTS;

D O I：

10.1002/anie.201607176

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity, and even reaction pathway, of excited states can be tuned by proton-coupled electron transfer (PCET). The triplet state of benzophenone functionalized with a Bronsted acid ((3)*BP-COOH) showed a more powerful oxidation capability over the simple triplet state of benzophenone ((3)*BP). (3)* BP-COOH could remove an electron from benzene at the rate of 8.0 x 10(5) M-1 s(-1), in contrast to the reactivity of (3)*BP which was inactive towards benzene oxidation. The origin of this great enhancement on the ability of the excited states to remove electrons from substrates is attributed to the intramolecular Bronsted acid, which enables the reductive quenching of (3)*BP by concerted electron-proton transfer.

引用

页码：13132 / 13136

页数：5

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