Tetrametallic Copper Complex to Nanoscale Copper: Selective and Switchable Dehydrogenation‐Hydrogenation under Light

Abstract

Discrete photoactive ultrafine nanocluster of copper with less than hundreds of atoms comprising stimuli-responsive switchable redox-active states is highly desired to control two different antagonistic reactions. Herein, we disclosed mixed-valent tetra metallic copper complex ( C-1 ) of N-O-N Schiff base ligand, in which its five different Cu-Cu interaction was utilized for the generation of photoactive nanoscale copper [LCu(0) n , S-1 ] via the reduction of coordinated imine to the amine of C-1 . The presence of ligand providing stability and assist to homogenize the material ( S-1 ) in the organic solvent. It showed stimuli (O 2 /light) responsive switchable performance between its reduced ( S-1 ) and oxidized [LCu(0) n-m CuO m , S-2 ] state and serve as highly and poorly active (bi-state, relative rate > 5-12 fold) catalyst for dehydrogenation of alcohols to aldehydes and hydrogenation of nitroaromatics to amino aromatics under the light.