Synthesis and characterization of a series of [M2(β-SiW8O31)2]n− clusters and mechanistic insight into the reorganization of {β-SiW8O31} into {α-SiW9O34}

Winter, R. S., Long, D.-L. and Cronin, L. (2015) Synthesis and characterization of a series of [M2(β-SiW8O31)2]n− clusters and mechanistic insight into the reorganization of {β-SiW8O31} into {α-SiW9O34}. Inorganic Chemistry, 54(8), pp. 4151-4155. (doi:10.1021/acs.inorgchem.5b00405)

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Abstract

Lacunary polyoxometalates of low nuclearity are difficult to synthesize in isolation. We report the facile synthesis of six {M2(B-β-SiW8O31)2} clusters (M = Co/Mn/Ni/Zn/Cu2+, Fe3+) that can be employed as building blocks for the formation of larger architectures. We show for the first time that such {B-β-SiW8O31} lacunae are capable of reorganizing into larger Keggin lacunary species even in the absence of an external source of tungstate. We hypothesize, based on electrospray ionization mass spectrometry evidence obtained, not only that such a transformation is only possible via an initial decomposition of the {SiW8} precursor into a {SiW6}-based intermediate but also that it is this {SiW6} species that acts as the template for the growth of the larger fragments.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Winter, Mr Ross and Long, Dr De Liang and Cronin, Professor Leroy
Authors: Winter, R. S., Long, D.-L., and Cronin, L.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Inorganic Chemistry
Publisher:American Chemical Society
ISSN:0020-1669
ISSN (Online):1520-510X

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
503291Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular LimitLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/H024107/1CHEM - CHEMISTRY
503295Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular LimitLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/H024107/1CHEM - CHEMISTRY