Lockey, D., Mathis, C., Miras, H. N. and Cronin, L. (2022) Investigating the autocatalytically driven formation of Keggin-based polyoxometalate clusters. Matter, 5(1), pp. 302-313. (doi: 10.1016/j.matt.2021.11.030)
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Abstract
The term self-assembly is used to describe the formation of many molecules and supramolecular architectures, but often, the precise mechanism is neglected. Here, we have investigated the kinetics of the self-assembly of the simplest heteropolyoxoanion, the Keggin ion [XMo12O40]x–. This study used variable temperature UV/vis spectroscopy to show that the Keggin ion can catalyze its own formation via an autocatalytic cycle. Kinetic investigations with real-time monitoring of the [XMo12O40]x– family’s formation reaction revealed key traits of autocatalytic systems, including kinetic saturation and concentration dependence of the incubation period. We explored the effect of the heteroatom on the kinetics of the autocatalytic process by investigating and comparing the formation rates of {AsMo12} and {SiMo12}. Finally, real-time electrospray ionization mass spectrometry studies of the reaction mixtures assist in the identification of the species involved in the formation process of the Keggin species, and these were explored using a stochastic model, which confirms our experimental observations.
Item Type: | Articles |
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Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Mathis, Dr Cole and Moiras, Professor Haralampos and Cronin, Professor Lee and Lockey, David |
Authors: | Lockey, D., Mathis, C., Miras, H. N., and Cronin, L. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Matter |
Publisher: | Elsevier (Cell Press) |
ISSN: | 2590-2393 |
ISSN (Online): | 2590-2385 |
Published Online: | 17 December 2021 |
Copyright Holders: | Copyright © 2021 Elsevier Inc. |
First Published: | First published in Matter 5(1): 302-313 |
Publisher Policy: | Reproduced in accordance with the publisher copyright policy |
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