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四电子在三联苯(双)二硫化物上的积累。

Accumulation of Four Electrons on a Terphenyl (Bis)disulfide.

机构信息

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.

出版信息

Chemistry. 2022 Dec 27;28(72):e202202386. doi: 10.1002/chem.202202386. Epub 2022 Nov 9.


DOI:10.1002/chem.202202386
PMID:36351246
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10098965/
Abstract

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.

摘要

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。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/d4c596f7cf65/CHEM-28-0-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/e16ad55648df/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/dd38ef9bc5d7/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/71064f97786b/CHEM-28-0-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/639ae059e91b/CHEM-28-0-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/62d1549a4053/CHEM-28-0-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/f6efcbe68f46/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/d4c596f7cf65/CHEM-28-0-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/e16ad55648df/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/dd38ef9bc5d7/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/71064f97786b/CHEM-28-0-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/639ae059e91b/CHEM-28-0-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/62d1549a4053/CHEM-28-0-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/f6efcbe68f46/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e3c7/10098965/d4c596f7cf65/CHEM-28-0-g007.jpg

相似文献

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Accumulation of Four Electrons on a Terphenyl (Bis)disulfide.

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[6]
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[7]
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[8]
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[9]
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[10]
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本文引用的文献

[1]
Recent Advances and Perspectives in Photodriven Charge Accumulation in Molecular Compounds: A Mini Review.

Energy Fuels. 2021-12-2

[2]
Visible Light Generation of a Microsecond Long-Lived Potent Reducing Agent.

J Am Chem Soc. 2022-4-27

[3]
Active repair of a dinuclear photocatalyst for visible-light-driven hydrogen production.

Nat Chem. 2022-5

[4]
A Bioinspired Disulfide/Dithiol Redox Switch in a Rhenium Complex as Proton, H Atom, and Hydride Transfer Reagent.

J Am Chem Soc. 2021-4-28

[5]
Photocatalytic hydrogen evolution using a Ru(ii)-bound heteroaromatic ligand as a reactive site.

Dalton Trans. 2020-12-21

[6]
Photoinduced Charge Accumulation and Prolonged Multielectron Storage for the Separation of Light and Dark Reaction.

J Am Chem Soc. 2020-9-16

[7]
Aryl dechlorination and defluorination with an organic super-photoreductant.

Photochem Photobiol Sci. 2020-8-1

[8]
Oligophenyls with Multiple Disulfide Bridges as Higher Homologues of Dibenzo[c,e][1,2]dithiin: Synthesis and Application in Lithium-Ion Batteries.

Chemistry. 2020-6-26

[9]
Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands.

Inorg Chem. 2020-4-6

[10]
Electron Storage System Based on a Two-Way Inversion of Redox Potentials.

J Am Chem Soc. 2020-3-18

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