Anisotropic polyoxometalate cages assembled via layers of heteroanion templates

Zheng, Q., Kupper, M., Xuan, W., Oki, H., Tsunashima, R., Long, D.-L. and Cronin, L. (2019) Anisotropic polyoxometalate cages assembled via layers of heteroanion templates. Journal of the American Chemical Society, 141(34), pp. 13479-13486. (doi:10.1021/jacs.9b04533) (PMID:31295408) (PMCID:PMC6716119)

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Abstract

The synthesis of anisotropic redox-active polyoxometalates (POMs) that can switch between multiple states is critical for understanding the mechanism of assembly of structures with a high aspect ratio, as well as for their application in electronic devices. However, a synthetic methodology for the controlled growth of such clusters is lacking. Here we describe a strategy, using the heteroanion-directed assembly, to produce a family of ten multi-layered anisotropic POM cages templated redox-active pyramidal heteroanions with the composition [W16Mo2O54(XO3)]n-,[W21Mo3O75(XO3)2]m-,[W26Mo4O93(XO3)3]o- for the single, double and triple layered clusters respectively. It was found that the introduction of reduced molybdate is essential for self-assembly of and results in mixed-metal (W/Mo) and mixed-valence (WVI/MoV) POM cages, as confirmed by an array of analytical techniques. To probe the archetype in detail, a tetrabutyl ammonium (TBA) salt derivative of a fully oxidized two-layered cage is produced as a model structure to confirm that all the cages are a statistical mixture of isostructures with variable ratios of W/Mo. Finally, it was found that multi-layered POM cages exhibit dipolar relaxations due to the presence of the mixed valence WVI/MoV metal centers, demonstrating their potential use for electronic materials.

Item Type:Articles
Additional Information:LC thanks the Royal Society / Wolfson Foundation for a Merit Award. RT and DL thank JSPS for awarding an Invitation Fellowship. We thank the Diamond Light Source for time on Beamline I19 under the proposal MT18953. We would also like to thank A. Bubliaus-kas and E. Nicholson of University of Glasgow for assistance with compound synthesis and analysis.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Xuan, Mr Weimin and Zheng, Ms Qi and Tsunashima, Dr Ryo and Long, Dr Deliang and Cronin, Professor Lee and Kupper, Manuel
Authors: Zheng, Q., Kupper, M., Xuan, W., Oki, H., Tsunashima, R., Long, D.-L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:11 July 2019
Copyright Holders:Copyright © 2019 American Chemical Society
First Published:First published in Journal of the American Chemical Society 141(34):13479-13486
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
616021Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
599451Microscale Chemically Reactive Electronic AgentsLeroy CroninEuropean Commission (EC)FP7 ICT MICRE318671CHEM - CHEMISTRY
685741SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467CHEM - CHEMISTRY

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