Electronic Structure and Photoactivity of Organoarsenic Hybrid Polyoxometalates

Kibler, Alexander J.; Tsang, Nicole; Winslow, Max; Argent, Stephen P.; Lam, Hon Wai; Robinson, David; Newton, Graham N.

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.

Citation

Kibler, A. J., Tsang, N., Winslow, M., Argent, S. P., Lam, H. W., Robinson, D., & Newton, G. N. (2023). Electronic Structure and Photoactivity of Organoarsenic Hybrid Polyoxometalates. Inorganic Chemistry, 62(8), 3585-3591. https://doi.org/10.1021/acs.inorgchem.2c04249

• Journal Article Type: Article
• Acceptance Date: Jan 17, 2023
• Online Publication Date: Feb 10, 2023
• Publication Date: Feb 27, 2023
• Deposit Date: Feb 17, 2023
• Publicly Available Date: Feb 21, 2023
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Electronic ISSN: 1520-510X
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 62
• Issue: 8
• Pages: 3585-3591
• DOI: https://doi.org/10.1021/acs.inorgchem.2c04249
• Keywords: Inorganic Chemistry; Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/17385023
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c04249