Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.
University of Göttingen, Institute of Inorganic Chemistry, Tammannstrasse 4, 37077, Göttingen, Germany.
Chemistry. 2022 Dec 27;28(72):e202202386. doi: 10.1002/chem.202202386. Epub 2022 Nov 9.
The activation of N , CO or H O to energy-rich products relies on multi-electron transfer reactions, and consequently it seems desirable to understand the basics of light-driven accumulation of multiple redox equivalents. Most of the previously reported molecular acceptors merely allow the storage of up to two electrons. We report on a terphenyl compound including two disulfide bridges, which undergoes four-electron reduction in two separate electrochemical steps, aided by a combination of potential compression and inversion. Under visible-light irradiation using the organic super-electron donor tetrakis(dimethylamino)ethylene, a cascade of light-induced reaction steps is observed, leading to the cleavage of both disulfide bonds. Whereas one of them undergoes extrusion of sulfur to result in a thiophene, the other disulfide is converted to a dithiolate. These insights seem relevant to enhance the current fundamental understanding of photochemical energy storage.
N、CO 或 H O 向富含能量产物的激活依赖于多电子转移反应,因此似乎有必要了解光驱动积累多个氧化还原当量的基本原理。以前报道的大多数分子受体只能储存多达两个电子。我们报告了一种包括两个二硫键的三联苯化合物,在电位压缩和反转的组合作用下,它通过两个独立的电化学步骤经历了四电子还原。在使用有机超电子供体四(二甲氨基)乙烯的可见光照射下,观察到一系列光诱导反应步骤,导致两个二硫键均断裂。其中一个二硫键经历硫的挤出以生成噻吩,而另一个二硫键则转化为二硫代物。这些见解似乎有助于增强对光化学储能的当前基本理解。
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