Tuning Excited-State Reactivity by Proton-Coupled Electron Transfer
Tuning Excited-State Reactivity by Proton-Coupled Electron Transfer
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通过质子耦合电子转移调节激发态反应性
DOI：
10.1002/anie.201607176
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
Zhang Ming-Tian
中科院分区：
文献类型：
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作者：
Li Han;Zhang Ming-Tian
激发态的反应性，甚至反应途径可以通过质子耦合电子转移（PCET）来调节。与简单的三重态二苯甲酮（3*BP）相比，三重态二苯甲酮（3* BP-COOH）具有更强的氧化能力。3 * BP-COOH可以以8.0× 105 m − 1 s −1的速率从苯上去除一个电子，而3 *BP对苯的氧化反应是惰性的。这种激发态从底物中移除电子的能力的极大增强归因于分子内的Brønsted酸，其通过协同的电子-质子转移使3 *BP还原猝灭。
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 Brønsted 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 8.0×105m−1s−1, in contrast to the reactivity of3*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 Brønsted acid, which enables the reductive quenching of3*BP by concerted electron–proton transfer.