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On the origins of nonradiative excited state relaxation in aryl sulfoxides relevant to fluorescent chemosensing


Kathayat, Rahul S; Yang, Lijun; Sattasathuchana, Tosaporn; Zoppi, Laura; Baldridge, Kim K; Linden, Anthony; Finney, Nathaniel S (2016). On the origins of nonradiative excited state relaxation in aryl sulfoxides relevant to fluorescent chemosensing. Journal of the American Chemical Society, 138(49):15889-15895.

Abstract

We provide herein a mechanistic analysis of aryl sulfoxide excited state processes, inspired by our recent report of
aryl sulfoxide based fluorescent chemosensors. The use of aryl sulfoxides as reporting elements in chemosensor development is a significant deviation from previous approaches, and thus warrants closer examination. We demonstrate that metal ion binding suppresses nonradiative excited state decay by blocking formation of a previously unrecognized charge transfer excited state, leading to fluorescence enhancement. This charge transfer state derives from the initially formed locally excited state followed by intramolecular charge transfer to form a sulfoxide radical cation/aryl radical anion pair. With the aid of computational studies, we map out ground and excited state potential energy surface details for aryl sulfoxides, and conclude that fluorescence enhancement is almost entirely the result of excited state effects. This work expands previous proposals that excited state pyramidal inversion is the major nonradiative decay pathway for aryl sulfoxides. We show that pyramidal inversion is indeed relevant, but that an additional and dominant nonradiative pathway must also exist. These conclusions have implications for the design of next generation sulfoxide based fluorescent chemosensors.

Abstract

We provide herein a mechanistic analysis of aryl sulfoxide excited state processes, inspired by our recent report of
aryl sulfoxide based fluorescent chemosensors. The use of aryl sulfoxides as reporting elements in chemosensor development is a significant deviation from previous approaches, and thus warrants closer examination. We demonstrate that metal ion binding suppresses nonradiative excited state decay by blocking formation of a previously unrecognized charge transfer excited state, leading to fluorescence enhancement. This charge transfer state derives from the initially formed locally excited state followed by intramolecular charge transfer to form a sulfoxide radical cation/aryl radical anion pair. With the aid of computational studies, we map out ground and excited state potential energy surface details for aryl sulfoxides, and conclude that fluorescence enhancement is almost entirely the result of excited state effects. This work expands previous proposals that excited state pyramidal inversion is the major nonradiative decay pathway for aryl sulfoxides. We show that pyramidal inversion is indeed relevant, but that an additional and dominant nonradiative pathway must also exist. These conclusions have implications for the design of next generation sulfoxide based fluorescent chemosensors.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Chemosensing, Fluorescence, Sulfoxides
Language:English
Date:2016
Deposited On:21 Dec 2016 16:07
Last Modified:15 Jan 2017 06:27
Publisher:American Chemical Society (ACS)
ISSN:0002-7863
Funders:Department of Chemistry (University of Zurich), Research Priority Program LightChEC (University of Zurich), School of Pharmaceutical Science and Technology (Tianjin University), National Basic Research Program of China (2015CB856500), Qian Ren Scholar Program of China, Synergetic Innovation Center of Chemical Science and Engineering (Tianjin University)
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in J. Am. Chem. Soc, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.6b00572.
Publisher DOI:https://doi.org/10.1021/jacs.6b00572
PubMed ID:27809511

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