Following the reaction of heteroanions inside a {W18O56} polyoxometalate nanocage by NMR spectroscopy and mass spectrometry

Zheng, Q., Vila-Nadal, L. , Busche, C., Mathieson, J. S., Long, D.-L. and Cronin, L. (2015) Following the reaction of heteroanions inside a {W18O56} polyoxometalate nanocage by NMR spectroscopy and mass spectrometry. Angewandte Chemie (International Edition), 127(27), pp. 8006-8010. (doi:10.1002/ange.201502295)

Zheng, Q., Vila-Nadal, L. , Busche, C., Mathieson, J. S., Long, D.-L. and Cronin, L. (2015) Following the reaction of heteroanions inside a {W18O56} polyoxometalate nanocage by NMR spectroscopy and mass spectrometry. Angewandte Chemie (International Edition), 127(27), pp. 8006-8010. (doi:10.1002/ange.201502295)

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Abstract

By incorporating phosphorus(III)-based anions into a polyoxometalate cage, a new type of tungsten-based unconventional Dawson-like cluster, [W18O56(HPIIIO3)2(H2O)2]8−, was isolated, in which the reaction of the two phosphite anions [HPO3]2− within the {W18O56} cage could be followed spectroscopically. As well as full X-ray crystallographic analysis, we studied the reactivity of the cluster using both solution-state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerize to form a weakly interacting (O3PH⋅⋅⋅HPO3) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two PIII template moieties to form PV centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells–Dawson {W18O54} cluster.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Busche, Dr Christoph and Long, Dr De Liang and Mathieson, Dr Jennifer and Vila-Nadal, Dr Laia and Cronin, Professor Leroy
Authors: Zheng, Q., Vila-Nadal, L., Busche, C., Mathieson, J. S., Long, D.-L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Angewandte Chemie (International Edition)
Publisher:Wiley - V C H Verlag GmbH & Co. KGaA
ISSN:1433-7851
ISSN (Online):1521-3757
Copyright Holders:Copyright © 2015 The Authors
First Published:First published in Angewandte Chemie (International Edition) 127(27):8006-8010
Publisher Policy:Reproduced under a Creative Commons License

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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