Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Zeng, Hongfei; Pérez-Sánchez, Juan B.; Eckdahl, Christopher T.; Liu, Pufan; Chang, Woo Je; Weiss, Emily A.; Kalow, Julia A.; Yuen-Zhou, Joel; Stern, Nathaniel P.

doi:10.1021/jacs.3c04254

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Journal Article · Tue Aug 29 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c04254· OSTI ID:3029273

Zeng, Hongfei ^[1]; Pérez-Sánchez, Juan B. ^[2]; Eckdahl, Christopher T. ^[1]; Liu, Pufan ^[1]; Chang, Woo Je ^[1]; ^[1]; ^[1]; ^[2]; ^[1]

Northwestern University, Evanston, IL (United States)
University of California−San Diego, La Jolla, CA (United States)

Most photochemistry occurs in the regime of weak light–matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light–matter interactions between an optical field and multiple molecules lead to collective hybrid light–matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. Here, the effect of strong light–matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light–matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: National Science Foundation Graduate Research Fellowship; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021314

Other Award/Contract Number:: DGE-1842165

OSTI ID:: 3029273

Alternate ID(s):: OSTI ID: 2421888

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 36 Vol. 145; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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