π‐Bridge Substitution in DASAs: The Subtle Equilibrium between Photochemical Improvements and Thermal Control
Authors
García Iriepa, CristinaIdentifiers
Permanent link (URI): http://hdl.handle.net/10017/59904DOI: 10.1002/chem.202004988
ISSN: 1521-3765
Date
2021-03-01Academic Departments
Universidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química
Teaching unit
Unidad docente Química Analítica e Ingeniería Quimica
Bibliographic citation
Chemistry a European Journal, 2021, v. 27, n. 13, p. 4420-4429
Keywords
DASA
photochemistry
photoswitches
thermal equilibrium
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/aceptedVersion
Rights
Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
© Wiley
Access rights
info:eu-repo/semantics/openAccess
Abstract
Donor-acceptor Stenhouse adducts (DASAs) are playing an outstanding role as innovative and versatile photoswitches. Until now, all the efforts have been spent on modifying the donor and acceptor moieties to modulate the absorption energy and improve the cyclization and reversion kinetics. However, there is a strong dependence on specific structural modifications and a lack of predictive behavior, mostly owing to the complex photoswitching mechanism. Here, by means of a combined experimental and theoretical study, the effect of chemical modification of the pi-bridge linking the donor and acceptor moieties is systematically explored, revealing the significant impact on the absorption, photocyclization, and relative stability of the open form. In particular, a position along the pi-bridge is found to be the most suited to redshift the absorption while preserving the cyclization. However, thermal back-reaction to the initial isomer is blocked. These effects are explained in terms of an increased acceptor capability offered by the pi-bridge substituent that can be modulated. This strategy opens the path toward derivatives with infra-red absorption and a potential anchoring point for further functionalization.
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Brdge_Martinez_Chemistry_2021.pdf | 1.345Mb |
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