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敏化剂-催化剂-敏化剂三联体的电荷积累和多电子光氧化还原化学。

Charge Accumulation and Multi-Electron Photoredox Chemistry with a Sensitizer-Catalyst-Sensitizer Triad.

机构信息

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

出版信息

Chemistry. 2018 Sep 20;24(53):14084-14087. doi: 10.1002/chem.201804037. Epub 2018 Aug 27.

Abstract

Photoinduced electron transfer in donor-sensitizer-acceptor compounds usually leads to simple electron-hole pairs, and photoredox catalysis typically relies on single-electron transfer (SET) events. This work reports on a molecular triad able to accumulate two electrons on a central dibenzo[1,2]dithiin moiety flanked by two peripheral Ru photosensitizers. Under continuous illumination, the doubly reduced form of the dibenzo[1,2]dithiin undergoes thiolate-disulfide exchange with an aliphatic disulfide substrate, thereby acting as a two-electron catalyst after two initial SET events with triethylamine at the Ru sensitizers. The use of a relatively simple triad for coupling two separate SET processes to a subsequent two-electron reduction is an important conceptual advance from photoinduced SET and light-driven charge accumulation towards multi-electron photoredox catalysis. This is relevant for artificial photosynthesis and light-driven multi-electron chemistry in general.

摘要

供体-敏化剂-受体化合物中的光诱导电子转移通常导致简单的电子-空穴对,而光氧化还原催化通常依赖于单电子转移 (SET) 事件。这项工作报道了一种分子三联体,它能够在两个外围 Ru 敏化剂所包围的中央二苯并[1,2]二噻吩部分上累积两个电子。在连续光照下,二苯并[1,2]二噻吩的双还原形式与脂肪族二硫化物底物进行硫醇-二硫化物交换,因此在 Ru 敏化剂上与三乙胺进行两个初始 SET 事件后,作为两电子催化剂。使用相对简单的三联体将两个单独的 SET 过程耦合到随后的两电子还原是从光诱导 SET 和光驱动电荷积累到多电子光氧化还原催化的重要概念进展。这对于人工光合作用和一般的光驱动多电子化学都很重要。

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