TY - JOUR
T1 - Tuning the Photoisomerization Mechanism of Oxindole Switches with Electron-Donating Substituents
AU - Mgbukwu, Matthew
AU - Fu, Xingjie
AU - Peshkov, Roman Yu
AU - Doellerer, Daniel
AU - Granados Buitrago, Camilo
AU - Feringa, Ben L
AU - Haacke, Stefan
AU - Crespi, Stefano
AU - Léonard, Jérémie
PY - 2025/4/17
Y1 - 2025/4/17
N2 - This study investigates the photoreaction mechanism of a hydroxy-substituted oxindole photoswitch using femtosecond transient absorption, fluorescence up-conversion, and computational chemistry. Deprotonation of the hydroxyl group enhances the push-pull character in the molecule, allowing tuning of the photoisomerization mechanism from a precessional to an axial motion. The neutral form of the switch exhibits longer excited-state lifetimes, while the anionic form decays rapidly within 200 fs. Computational models show that deprotonation increases the charge transfer and accessibility to conical intersections. This work highlights how varying the electron-donating strength of a substituent in a push-pull photoswitch tunes the photoreaction mechanism in designing photoswitches.
AB - This study investigates the photoreaction mechanism of a hydroxy-substituted oxindole photoswitch using femtosecond transient absorption, fluorescence up-conversion, and computational chemistry. Deprotonation of the hydroxyl group enhances the push-pull character in the molecule, allowing tuning of the photoisomerization mechanism from a precessional to an axial motion. The neutral form of the switch exhibits longer excited-state lifetimes, while the anionic form decays rapidly within 200 fs. Computational models show that deprotonation increases the charge transfer and accessibility to conical intersections. This work highlights how varying the electron-donating strength of a substituent in a push-pull photoswitch tunes the photoreaction mechanism in designing photoswitches.
U2 - 10.1021/acs.jpcb.4c06856
DO - 10.1021/acs.jpcb.4c06856
M3 - Article
C2 - 40197135
SN - 1520-6106
VL - 129
SP - 3839
EP - 3850
JO - The Journal of Physical Chemistry. B: Materials, Surfaces, Interfaces, & Biophysical
JF - The Journal of Physical Chemistry. B: Materials, Surfaces, Interfaces, & Biophysical
IS - 15
M1 - 4c06856
ER -