A cobalt redox switch driving alcohol dehydrogenation by redox coupled molecular swing  

作　　者：Guoling Li Yang Liu Wei Wang Zhu Zhuo Yougui Huang 

机构地区：[1]CAS Key Laboratory of Design and Assembly of Functional Nanostructures,and Fujian Provincial Key Laboratory of Nanomaterials,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Xiamen 361021,China [2]Xiamen Institute of Rare Earth Materials,Haixi Institute,Chinese Academy of Sciences,Xiamen 361021,China [3]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China

出　　处：《Chinese Chemical Letters》2023年第6期459-462,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21871262,21805275 and 21901242);the Natural Science Foundation of Fujian Province(No.2019J01130);the Recruitment Program of Global Youth Experts。

摘　　要：Developing redox switches that not only perform specific mechanical movements but also drive important chemical reactions is important but a great challenge.Herein,we report a redox pair of cobalt species(Co^(Ⅲ)/Co^(Ⅱ))that switches through photo-dehydrogenation of alcohol and hydrogenation of azo-ligand.The cobalt species is equipped with a flexible azo-ligand containing two bulky planar substituents.A planar oxidated sate(Co^(Ⅲ)species)can be photo-reduced to a saddle-like reduced state(Co^(Ⅱ))with alcohol molecules as electron donors,and in turn the Co^(Ⅲ)species can be recovered with azo-ligand as oxidant under acidic surrounding.Both the redox states of the pair are isolated and characterized by single crystal X-ray diffraction.In the switching cycle,alcohol is oxidized to aldehyde by azo-ligand through proton coupled electron transfer and the cobalt complex acts as a redox catalyst.These results provide important insights into alcohol dehydrogenation catalyzed by redox complexes.

关 键 词：Redox switch Alcohol dehydrogenation Azo-ligand hydrogenation Cobalt complex Mechanical motion 

分 类 号：O641.4[理学—物理化学] O621.251[理学—化学]