Rational Design of Triplet Sensitizers for the Transfer of Excited State Photochemistry from UV to Visible

Elliott, Luke D.; Kayal, Surajit; George, Michael W.; Booker-Milburn, Kevin

Abstract

Time Dependent Density Functional Theory has been used to assist the design and synthesis of a series thioxanthone triplet sensitizers. Calculated energies of the triplet excited state (ET) informed both the type and position of auxochromes placed on the thioxanthone core, enabling fine-tuning of the UV-vis absorptions and associated triplet energies. The calculated results were highly consistent with experimental observation in both the order of the λmax and ET values. The synthesized compounds were then evaluated for their efficacies as triplet sensitizers in a variety of UV and visible light preparative photochemical reactions. The results of this study exceeded expectations; in particular [2 + 2] cycloaddition chemistry that had previously been sensitized in the UV was found to undergo cycloaddition at 455 nm (blue) with a 2- to 9-fold increase in productivity (g/h) relative to input power. This study demonstrates the ability of powerful modern computational methods to aid in the design of successful and productive triplet sensitized photochemical reactions.

Citation

Elliott, L. D., Kayal, S., George, M. W., & Booker-Milburn, K. (2020). Rational Design of Triplet Sensitizers for the Transfer of Excited State Photochemistry from UV to Visible. Journal of the American Chemical Society, 142(35), 14947-14956. https://doi.org/10.1021/jacs.0c05069

• Journal Article Type: Article
• Acceptance Date: Aug 4, 2020
• Online Publication Date: Aug 19, 2020
• Publication Date: Sep 2, 2020
• Deposit Date: Aug 26, 2020
• Publicly Available Date: Aug 20, 2021
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Peer Reviewed: Peer Reviewed
• Volume: 142
• Issue: 35
• Pages: 14947-14956
• DOI: https://doi.org/10.1021/jacs.0c05069
• Keywords: Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis
• Public URL: https://nottingham-repository.worktribe.com/output/4847000
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.0c05069
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.0c05069.