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 |
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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 Kupper, Manuel and Long, Dr Deliang and Cronin, Professor Lee |
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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