Chirality meets visible-light photocatalysis in a molecular cerium vanadium oxide cluster

The first example of a molecular cerium vanadium oxide photocatalyst is presented. A cerium vanadium oxide cluster, (nBu(4)N)(2)- [(Ce(dmso)(3))(2)(VV11O33Cl)-V-IV-O-V] x 2DMSO (1), was obtained by bottom-up self-assembly. The compound exhibits high visible-light photooxidative activity towards indigo with quantum efficiencies >10%. Initial mechanistic studies of the photooxidation reaction are presented. The structure of compound 1 is based on chiral, C-2-symmetric cluster anions and both enantiomers are present in the crystal lattice. Retrosynthetic analysis suggests that chiral building blocks are spontaneously formed by symmetry breaking during self-assembly. The assembly of 1 based on the chiral building blocks is discussed conceptually. Consequences of this assembly mechanism for the development of chiral molecular catalysts and photocatalysts are described.