title: Mixed-Valent Mn16-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties.
abstract: The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [Mn(III)10Mn(II)6O6(OH)6(PO4)4(A-α-SiW9O34)4](28-) (1) and [Mn(III)4Mn(II)12(OH)12(PO4)4(A-α-SiW9O34)4](28-) (2) have been prepared by reaction of the trilacunary Keggin precursor [A-α-SiW9O34](10-) with either Mn(OOCCH3)3·2H2O (for 1) or MnCl2·4H2O (for 2), in aqueous phosphate solution at pH 9. Polyanions 1 and 2 comprise mixed-valent, cationic {Mn(III)10Mn(II)6O6(OH)6}(24+) and {Mn(III)4Mn(II)12(OH)12}(24+) cores, respectively, encapsulated by four phosphate groups and four {SiW9} units in a tetrahedral fashion. Both polyanions were structurally and compositionally characterized by single-crystal XRD, IR, thermogravimetric analysis, and X-ray absorption spectroscopy. Furthermore, studies were performed probing the magnetic, electrochemical, oxidation catalytic, and Li-ion battery performance of 1 and 2.
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Ali
authors.initials: A
authors.lastname: Haider
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Masooma
authors.initials: M
authors.lastname: Ibrahim
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.|Department of Chemistry, Faculty of Sciences, University of Balamand , P.O. Box 100, Tripoli, Lebanon.
authors.forename: Bassem S
authors.initials: BS
authors.lastname: Bassil
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Akina M
authors.initials: AM
authors.lastname: Carey
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Anh Nguyen
authors.initials: AN
authors.lastname: Viet
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Xiaolin
authors.initials: X
authors.lastname: Xing
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Wassim W
authors.initials: WW
authors.lastname: Ayass
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Juan F
authors.initials: JF
authors.lastname: Miñambres
authors.affiliation: Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences , 100190, Beijing, China.
authors.forename: Rongji
authors.initials: R
authors.lastname: Liu
authors.affiliation: Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences , 100190, Beijing, China.
authors.forename: Guangjin
authors.initials: G
authors.lastname: Zhang
authors.affiliation: Université Paris-Sud, Laboratoire de Chimie-Physique, UMR 8000 CNRS , Orsay, F-91405, France.
authors.forename: Bineta
authors.initials: B
authors.lastname: Keita
authors.affiliation: Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Valeriu
authors.initials: V
authors.lastname: Mereacre
authors.affiliation: Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.|Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) , Engesserstrasse 15, 76131 Karlsruhe, Germany.
authors.forename: Annie K
authors.initials: AK
authors.lastname: Powell
authors.affiliation: Department of Physics and Center of Physics and Chemistry of New Materials, Osnabrück University , D-49069 Osnabrück, Germany.
authors.forename: Kamil
authors.initials: K
authors.lastname: Balinski
authors.affiliation: Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Alpha T
authors.initials: AT
authors.lastname: N'Diaye
authors.affiliation: Department of Physics and Center of Physics and Chemistry of New Materials, Osnabrück University , D-49069 Osnabrück, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Küpper
authors.affiliation: TUM CREATE , 1 CREATE Way, #10-02 CREATE Tower, 138602 Singapore.|Department of Chemistry, Technische Universität München , Lichtenbergstraße 4, 85748 Garching, Germany.
authors.forename: Han-Yi
authors.initials: HY
authors.lastname: Chen
authors.affiliation: TUM CREATE , 1 CREATE Way, #10-02 CREATE Tower, 138602 Singapore.|Department of Chemistry, Technische Universität München , Lichtenbergstraße 4, 85748 Garching, Germany.|School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne, NE1 7RU, United Kingdom.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Stimming
authors.affiliation: Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Kortz