Malcolm, D. and Vilà-Nadal, L. (2023) Computational study into the effects of countercations on the [P₈W₄₈O₁₈₄]⁴⁰⁻ polyoxometalate wheel. ACS Organic and Inorganic Au, 3(5), pp. 274-282. (doi: 10.1021/acsorginorgau.3c00014)
![[img]](https://eprints.gla.ac.uk/style/images/fileicons/text.png) |
Text
302055.pdf - Published Version Available under License Creative Commons Attribution. 5MB |
Abstract
Porous metal oxide materials have been obtained from a ring-shaped macrocyclic polyoxometalate (POM) structural building unit, [P8W48O184]40–. This is a tungsten oxide building block with an integrated “pore” of 1 nm in diameter, which, when connected with transition metal linkers, can assemble frameworks across a range of dimensions and which are generally referred to as POMzites. Our investigation proposes to gain a better understanding into the basic chemistry of this POM, specifically local electron densities and locations of countercations within and without the aforementioned pore. Through a rigorous benchmarking process, we discovered that 8 potassium cations, located within the pore, provided us with the most accurate model in terms of mimicking empirical properties to a sufficient degree of accuracy while also requiring a relatively small number of computer cores and hours to successfully complete a calculation. Additionally, we analyzed two other similar POMs from the literature, [As8W48O184]40– and [Se8W48O176]32–, in the hopes of determining whether they could be similarly incorporated into a POMzite network; given their close semblance in terms of local electron densities and interaction with potassium cations, we judge these POMs to be theoretically suitable as POMzite building blocks. Finally, we experimented with substituting different cations into the [P8W48O184]40– pore to observe the effect on pore dimensions and overall reactivity; we observed that the monocationic structures, particularly the Li8[P8W48O184]32– framework, yielded the least polarized structures. This correlates with the literature, validating our methodology for determining general POM characteristics and properties moving forward.
| Item Type: | Articles |
|---|---|
| Additional Information: | Financial support for this work was provided by University of Glasgow and the Engineering and Physical Sciences Research Council Grants(EP/S030603/1; EP/V048341/1; EP/S031170/1), Royal Society of Chemistry RSC Hardship Grant(Covid-19).We thank the EPSRC Doctoral Training Parntertship (DTP)funding received by the University of Glasgow for Daniel Malcolm PhD studentship “Metal oxides by design”project2443457 (EP/R513222/; EP/T517896/1). We also thank the University of Glasgow(UofGla) Early Career Development Programme (ECDP) 2021, the UofGla Reinvigorating Research Scheme2022,and the School of Chemistry for long-lasting support. |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Vila-Nadal, Dr Laia and Malcolm, Mr Daniel |
| Creator Roles: | Malcolm, D.Formal analysis, Investigation, Methodology, Writing – original draft, Writing – review and editing Vila-Nadal, L.Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review and editing |
| Authors: | Malcolm, D., and Vilà-Nadal, L. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | ACS Organic and Inorganic Au |
| Publisher: | American Chemical Society |
| ISSN: | 2694-247X |
| ISSN (Online): | 2694-247X |
| Published Online: | 22 July 2023 |
| Copyright Holders: | Copyright © 2023 The Authors |
| First Published: | First published in ACS Organic and Inorganic Au 3(5):274-282 |
| Publisher Policy: | Reproduced under a Creative Commons license |
| Related URLs: |
University Staff: Request a correction | Enlighten Editors: Update this record
Funder and Project Information
Funder and Project Information