Tuning the Photoisomerization Mechanism of Oxindole Switches with Electron-Donating Substituents
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.
Authors
- Stefan Haacke (ORCID: https://orcid.org/0000-0002-6969-4667)
- Jérémie Léonard (ORCID: https://orcid.org/0000-0003-1809-3543)
- Daniel Doellerer (ORCID: https://orcid.org/0000-0001-8973-9968)
- Stefano Crespi (ORCID: https://orcid.org/0000-0002-0279-4903)
- Xing Fu
- Roman Yu. Peshkov (ORCID: https://orcid.org/0000-0002-6024-2031)
- Ben L. Feringa (ORCID: https://orcid.org/0000-0003-0588-8435)
- Matthew Mgbukwu
- Camilo Granados Buitrago
Institutions
- Uppsala University (SE)
- University of Groningen (NL)
- Institut de Physique et Chimie des Matériaux de Strasbourg (FR)
- Université de Strasbourg (FR)
Publication Details
- Journal
- The Journal of Physical Chemistry B
- Published
- 2025-04-08
- DOI
- https://doi.org/10.1021/acs.jpcb.4c06856
- Citations
- 5
- Primary Topic
- Photoreceptor and optogenetics research
- Type
- article
- Field-Weighted Citation Impact
- 4.55
Funders
- Göran Gustafssons Stiftelser
- Agence Nationale de la Recherche
- Institut National de la Santé et de la Recherche Médicale
- Rijksuniversiteit Groningen
- National Science Council
- Ministerie van Onderwijs, Cultuur en Wetenschap
- Université de Strasbourg
- Vetenskapsrådet
- Stiftelsen Lars Hiertas Minne
- Centre National de la Recherche Scientifique
- Uppsala Universitet
- Laboratoires d'excellence Nanostructures en Interaction avec leur Environnement
- Zernike Institute for Advanced Materials, Rijksuniversiteit Groningen