title: Chirality meets visible-light photocatalysis in a molecular cerium vanadium oxide cluster.
abstract: The first example of a molecular cerium vanadium oxide photocatalyst is presented. A cerium vanadium oxide cluster, (nBu4N)2[(Ce(dmso)3)2V(IV)V(V)11O33Cl] × 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, C2-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.
authors.affiliation: Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany. carsten.streb@uni-ulm.de.
authors.forename: Andrey
authors.initials: A
authors.lastname: Seliverstov
authors.forename: Carsten
authors.initials: C
authors.lastname: Streb