TY - JOUR
T1 - Control of Photoswitching Kinetics with Strong Light-Matter Coupling in a Cavity
AU - Zeng, Hongfei
AU - Pérez-Sánchez, Juan B.
AU - Eckdahl, Christopher T.
AU - Liu, Pufan
AU - Chang, Woo Je
AU - Weiss, Emily A.
AU - Kalow, Julia A.
AU - Yuen-Zhou, Joel
AU - Stern, Nathaniel P.
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/9/13
Y1 - 2023/9/13
N2 - 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. 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.
AB - 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. 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.
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U2 - 10.1021/jacs.3c04254
DO - 10.1021/jacs.3c04254
M3 - Article
C2 - 37643086
AN - SCOPUS:85171203393
SN - 0002-7863
VL - 145
SP - 19655
EP - 19661
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -