Electronic structure and photoactivity of organoarsenic hybrid polyoxometalates

Kibler, AJ, Tsang, N, Winslow, M ORCID: https://orcid.org/0000-0003-1985-0905, Argent, SP, Lam, HW, Robinson, D ORCID: https://orcid.org/0000-0003-2760-7163 and Newton, GN, 2023. Electronic structure and photoactivity of organoarsenic hybrid polyoxometalates. Inorganic Chemistry. ISSN 0020-1669

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Abstract

Organofunctionalization of polyoxometalates (POMs) allows the preparation of hybrid molecular systems with tunable electronic properties. Currently, there are only a handful of approaches that allow for the fine-tuning of POM frontier molecular orbitals in a predictable manner. Herein, we demonstrate a new functionalization method for the Wells–Dawson polyoxotungstate [P2W18O62]6– using arylarsonic acids which enables modulation of the redox and photochemical properties. Arylarsonic groups facilitate orbital mixing between the organic and inorganic moieties, and the nature of the organic substituents significantly impacts the redox potentials of the POM core. The photochemical response of the hybrid POMs correlates with their computed and experimentally estimated lowest unoccupied molecular orbital energies, and the arylarsonic hybrids are found to exhibit increased visible light photosensitivity comparable with that of arylphosphonic analogues. Arylarsonic hybridization offers a route to stable and tunable organic–inorganic hybrid systems for a range of redox and photochemical applications.

Item Type:	Journal article
Publication Title:	Inorganic Chemistry
Creators:	Kibler, A.J., Tsang, N., Winslow, M., Argent, S.P., Lam, H.W., Robinson, D. and Newton, G.N.
Publisher:	American Chemical Society (ACS)
Date:	10 February 2023
ISSN:	0020-1669
Identifiers:	Number Type 10.1021/acs.inorgchem.2c04249 DOI 1732214 Other
Rights:	©2023 The Authors. Published by American Chemical Society. This article is open access and uses a Creative Commons public use license, e.g., CC-BY or CC-BY-NC-ND.
Divisions:	Schools > School of Science and Technology
Record created by:	Linda Sullivan
Date Added:	14 Feb 2023 16:36
Last Modified:	14 Feb 2023 16:36
URI:	https://irep.ntu.ac.uk/id/eprint/48292

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