title: Visible-Light-Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster.
abstract: Photosynthetic water oxidation in plants occurs at an inorganic calcium manganese oxo cluster, which is known as the oxygen evolving complex (OEC), in photosystem II. Herein, we report a synthetic OEC model based on a molecular manganese vanadium oxide cluster, [Mn4 V4 O17 (OAc)3 ](3-) . The compound is based on a [Mn4 O4 ](6+) cubane core, which catalyzes the homogeneous, visible-light-driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V4 O13 ](6-) polyoxovanadate and three acetate ligands. When combined with the photosensitizer [Ru(bpy)3 ](2+) and the oxidant persulfate, visible-light-driven water oxidation with turnover numbers of approximately 1150 and turnover frequencies of about 1.75 s(-1) is observed. Electrochemical, mass-spectrometric, and spectroscopic studies provide insight into the cluster stability and reactivity. This compound could serve as a model for the molecular structure and reactivity of the OEC and for heterogeneous metal oxide water-oxidation catalysts.
authors.affiliation: Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Schwarz
authors.affiliation: Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
authors.forename: Johannes
authors.initials: J
authors.lastname: Forster
authors.affiliation: Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
authors.forename: McKenna K
authors.initials: MK
authors.lastname: Goetz
authors.affiliation: Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany.
authors.forename: Duygu
authors.initials: D
authors.lastname: Yücel
authors.affiliation: Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany.
authors.forename: Claudia
authors.initials: C
authors.lastname: Berger
authors.affiliation: Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany.
authors.forename: Timo
authors.initials: T
authors.lastname: Jacob
authors.affiliation: Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany. carsten.streb@uni-ulm.de.
authors.forename: Carsten
authors.identifier: 0000-0002-5846-1905
authors.initials: C
authors.lastname: Streb
keywords: manganese; polyoxometalates; polyoxovanadates; self-assembly; water oxidation