Control of the Photo-Isomerization Mechanism ...
Document type :
Article dans une revue scientifique: Article original
DOI :
PMID :
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Title :
Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts.
Author(s) :
Brazevic, S. [Auteur]
Nizinski, S. [Auteur]
Sliwa, Michel [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Abe, J. [Auteur]
Rode, M. F. [Auteur]
Burdzinski, G. [Auteur]
Nizinski, S. [Auteur]
Sliwa, Michel [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Abe, J. [Auteur]
Rode, M. F. [Auteur]
Burdzinski, G. [Auteur]
Journal title :
International Journal of Molecular Sciences
Abbreviated title :
Int J Mol Sci
Volume number :
21
Publication date :
2020-11-11
ISSN :
1422-0067
English keyword(s) :
time-resolved spectroscopy
reaction mechanisms
quantum chemical calculations
photophysics
photodynamics
photochromism
naphthopyran
bicycle-pedal isomerization
reaction mechanisms
quantum chemical calculations
photophysics
photodynamics
photochromism
naphthopyran
bicycle-pedal isomerization
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
English abstract : [en]
In the photochromic reactions of 3H-naphthopyrans, two colored isomers TC (transoid-cis) and TT (transoid-trans) are formed. In terms of optimized photo-switchable materials, synthetic efforts are nowadays evolving toward ...
Show more >In the photochromic reactions of 3H-naphthopyrans, two colored isomers TC (transoid-cis) and TT (transoid-trans) are formed. In terms of optimized photo-switchable materials, synthetic efforts are nowadays evolving toward developing 3H-naphthopyran derivatives that would not be able to photoproduce the long-living transoid-trans, TT, photoproduct. The substitution with a methoxy group at position 10 results in significant reduction of the TT isomer formation yield. The TC photophysics responsible for TT suppression were revealed here using a combination of multi-scale time resolved absorption UV-vis spectroscopy and ab initio calculations. The substitution changes the TC excited-state potential energy landscape, the bicycle-pedal isomerization path is favored over the rotation around a single double bond. The bicycle-pedal path is aborted in halfway to TT formation due to S1→S0 internal conversion populating back the TC species in the ground electronic state. This is validated by a shorter TC S1 state lifetime for methoxy derivative in comparison to that of the parent-unsubstituted compound (0.47 ± 0.05 ps vs. 0.87 ± 0.09 ps) in cyclohexane.Show less >
Show more >In the photochromic reactions of 3H-naphthopyrans, two colored isomers TC (transoid-cis) and TT (transoid-trans) are formed. In terms of optimized photo-switchable materials, synthetic efforts are nowadays evolving toward developing 3H-naphthopyran derivatives that would not be able to photoproduce the long-living transoid-trans, TT, photoproduct. The substitution with a methoxy group at position 10 results in significant reduction of the TT isomer formation yield. The TC photophysics responsible for TT suppression were revealed here using a combination of multi-scale time resolved absorption UV-vis spectroscopy and ab initio calculations. The substitution changes the TC excited-state potential energy landscape, the bicycle-pedal isomerization path is favored over the rotation around a single double bond. The bicycle-pedal path is aborted in halfway to TT formation due to S1→S0 internal conversion populating back the TC species in the ground electronic state. This is validated by a shorter TC S1 state lifetime for methoxy derivative in comparison to that of the parent-unsubstituted compound (0.47 ± 0.05 ps vs. 0.87 ± 0.09 ps) in cyclohexane.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
Administrative institution(s) :
Université de Lille
CNRS
CNRS
Collections :
Submission date :
2024-02-28T22:51:14Z
2024-03-12T15:37:37Z
2024-03-12T15:37:37Z
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