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Visible‐Light‐Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster

Schwarz, Benjamin et al.

Angewandte Chemie international edition. Volume 55:Issue 21 (2016); pp 6329-6333 -- Wiley-VCH Verlag GmbH

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  • Title:
    Visible‐Light‐Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster
  • Author: Schwarz, Benjamin;
    Forster, Johannes;
    Goetz, McKenna K.;
    Yücel, Duygu;
    Berger, Claudia;
    Jacob, Timo;
    Streb, Carsten
  • Found In: Angewandte Chemie international edition. Volume 55:Issue 21 (2016); pp 6329-6333
  • Journal Title: Angewandte Chemie international edition
  • Subjects: Chemistry--Periodicals; manganese--polyoxometalates--polyoxovanadates--self-assembly--water oxidation; Dewey: 540
  • Rights: legaldeposit
  • Publication Details: Wiley-VCH Verlag GmbH
  • Abstract: 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, [Mn4V4O17(OAc)3] 3− . The compound is based on a [Mn4O4] 6+ cubane core, which catalyzes the homogeneous, visible‐light‐driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V4O13] 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.

    Abstract :

    A molecular manganese vanadium oxidecluster was synthesized, characterized, and employed as a catalyst for visible‐light‐driven water oxidation. The compound is a molecular model for the oxygen evolving complex (OEC) in photosystem II and provides access to the S1, S2, and S3redox states of the water oxidation ("Kok") cycle.


  • Identifier: System Number: LDEAvdc_100076766097.0x000001; Journal ISSN: 1433-7851; 10.1002/anie.201601799
  • Publication Date: 2016
  • Physical Description: Electronic
  • Shelfmark(s): ELD Digital store

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