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Structure and properties of new gallium-containing polyoxotungstates with hexanuclear and tetranuclear cores


von Allmen, Kim; Car, Pierre-Emmanuel; Blacque, Olivier; Fox, Thomas; Müller, Rafael; Patzke, Greta R (2014). Structure and properties of new gallium-containing polyoxotungstates with hexanuclear and tetranuclear cores. Zeitschrift für Anorganische und Allgemeine Chemie, 640(5):781-789.

Abstract

A series of new gallium-containing silicotungstates was obtained from the one step reaction of the lacunary Na10[α-SiW9O34]·15H2O Keggin-type building block (SiW9) with gallium nitrate in aqueous solution. The sandwich-type polyoxotungstate [Ga6(H2O)x{α-SiW9O34(OH)y}2]n– (1) crystallizes first as a mixture of two similar polyoxometalates (1a and 1b), while [Ga4(H2O)2{α-SiW10O38}2]12– (2) is generated from the mother liquor in a second step. Both newly obtained polyoxometalates with tetra- and hexanuclear gallium cores were structurally characterized with a wide range of methods encompassing single crystal and powder X-ray diffraction techniques, FT-IR spectroscopy, and thermal analysis. The solution stability of both dimeric POMs K10[Ga6(H2O)3{α-SiW9O35(OH)2}2]·35.5H2O (1a) and K12[Ga4(H2O)2{α-SiW10O38}2]·30H2O (2) was investigated with 183W NMR and HR ESI mass spectrometry, and the electrochemical properties of both compounds were determined by cyclic voltammetry.

Abstract

A series of new gallium-containing silicotungstates was obtained from the one step reaction of the lacunary Na10[α-SiW9O34]·15H2O Keggin-type building block (SiW9) with gallium nitrate in aqueous solution. The sandwich-type polyoxotungstate [Ga6(H2O)x{α-SiW9O34(OH)y}2]n– (1) crystallizes first as a mixture of two similar polyoxometalates (1a and 1b), while [Ga4(H2O)2{α-SiW10O38}2]12– (2) is generated from the mother liquor in a second step. Both newly obtained polyoxometalates with tetra- and hexanuclear gallium cores were structurally characterized with a wide range of methods encompassing single crystal and powder X-ray diffraction techniques, FT-IR spectroscopy, and thermal analysis. The solution stability of both dimeric POMs K10[Ga6(H2O)3{α-SiW9O35(OH)2}2]·35.5H2O (1a) and K12[Ga4(H2O)2{α-SiW10O38}2]·30H2O (2) was investigated with 183W NMR and HR ESI mass spectrometry, and the electrochemical properties of both compounds were determined by cyclic voltammetry.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2014
Deposited On:20 Feb 2015 10:21
Last Modified:01 Jun 2017 04:35
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:0044-2313
Publisher DOI:https://doi.org/10.1002/zaac.201300669

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