An octanuclear Cu(ii) cluster with a bio-inspired Cu₄O₄ cubic fragment for efficient photocatalytic water oxidation

Abstract

An octanuclear Cu(ii) cluster [Cu8(dpk·OH)8(OAc)4](ClO4)4 was found to be an efficient homogeneous catalyst for photocatalytic water oxidation with an oxygen yield, TON and TOF of 35.6%, 178 and 3.6 s−1, respectively.

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

“…Subsequently, an octanuclear Cu(II) cluster [Cu 8 (dpk⋅OH) 8 (OAc) 4 ](ClO 4 ) 4 (dpk⋅OH=the monoanion of the hydrate) was reported by Ding's group. The cluster contains two Cu 4 O 4 cubic fragments (Figure ) . The centrosymmetric Cu 4 O 4 cubanes were doubly bridged by two anti‐ligands through two Cu atoms.…”

“… Crystal structure of [Cu 8 (dpk⋅OH) 8 (OAc) 4 ] 4+ . Color Code: Cu, green; C, gray; O, red; and N, blue …”

“…The cluster contains two Cu 4 O 4 cubic fragments ( Figure 2). [55] The centrosymmetric Cu 4 O 4 cubanes were doubly bridged by two anti-ligands through two Cu atoms. And each cubane was surrounded by four deprotonated oxygen atoms from the dpk·OH À ligands.…”

“…Color Code: Cu, green; C, gray; O, red; and N, blue. [55] O) 2 (PA) 8 (O i Pr) 16 ]. The Ti 52 cluster is the largest TOC reported to date and displays high H 2 production activity (398 μmol h À 1 g À 1 ).…”

Recent Progress in Visible Light Driven Water Oxidation Using Semiconductors Coupled with Molecular Catalysts

“…In spite of heterogeneous WOCs are easily obtained on a large scale and conveniently reused, homogeneous molecular water oxidation catalysts attract increasing attention for the advantages of high catalytic efficiencies, advantages in mechanism research and easy modification in structures . In the past decades, molecular catalysts were mainly applied to the dye‐sensitized systems containing molecular [Ru(bpy) 3 ] 2+ (bpy=2,2′‐bipyridine) or its derivatives as light harvester . A large number of transition‐metal (Fe, Co, Ni, Cu, Mn, Ru) substituted molecular catalysts were demonstrated to be excellent WOCs in molecular light harvester systems under visible light illumination.…”