Investigating the autocatalytically driven formation of Keggin-based polyoxometalate clusters

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
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Moiras, Dr Haralampos and Cronin, Professor Lee and Lockey, David and Mathis, Dr Cole
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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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
166449Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1Chemistry
190796Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1Chemistry
166779Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/I033459/1Chemistry
167864Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1Chemistry
172151SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467Chemistry