Exploiting Potential Inversion for Photoinduced Multielectron Transfer and Accumulation of Redox Equivalents in a Molecular Heptad,Journal of the American Chemical Society

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Exploiting Potential Inversion for Photoinduced Multielectron Transfer and Accumulation of Redox Equivalents in a Molecular Heptad
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-04-13 , DOI: 10.1021/jacs.8b02443
Julia Nomrowski ₁ , Oliver S. Wenger ₁

Affiliation

Photoinduced multielectron transfer and reversible accumulation of redox equivalents is accomplished in a fully integrated molecular heptad composed of four donors, two photosensitizers, and one acceptor. The second reduction of the dibenzo[1,2]dithiin acceptor occurs more easily than the first by 1.3 V, and this potential inversion facilitates the light-driven formation of a two-electron reduced state with a lifetime of 66 ns in deaerated CH3CN. The quantum yield for formation of this doubly charge-separated photoproduct is 0.5%. In acidic oxygen-free solution, the reduction product is a stable dithiol. Under steady-state photoirradiation, our heptad catalyzes the two-electron reduction of an aliphatic disulfide via thiolate-disulfide interchange. Exploitation of potential inversion for the reversible light-driven accumulation of redox equivalents in artificial systems is unprecedented and the use of such a charge-accumulated state for multielectron photoredox catalysis represents an important proof-of-concept.

中文翻译：

利用电位反转进行光致多电子转移和分子七联体中氧化还原当量的积累

光致多电子转移和氧化还原当量的可逆积累是在由四个供体、两个光敏剂和一个受体组成的完全集成的分子七联体中完成的。二苯并[1,2]二噻英受体的第二次还原比第一次还原更容易发生 1.3 V，并且这种电位反转有助于光驱动形成双电子还原态，脱气 CH3CN 中的寿命为 66 ns。形成这种双电荷分离光产物的量子产率为 0.5%。在酸性无氧溶液中，还原产物是稳定的二硫醇。在稳态光照射下，我们的七元组通过硫醇盐-二硫化物交换催化脂肪族二硫化物的双电子还原。

更新日期：2018-04-13

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