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Open AccessArticle

Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts

1
Faculty of Physics, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 2, 61-614 Poznan, Poland
2
Laboratoire de Spectroscopie pour les Interactions, la Réactivité et l’Environnement, LASIRE, CNRS, UMR 8516, Univ. Lille, 59000 Lille, France
3
Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan
4
Institute of Physics, Polish Academy of Sciences, Aleja Lotników 32/46, 02-668 Warsaw, Poland
*
Authors to whom correspondence should be addressed.
Int. J. Mol. Sci. 2020, 21(21), 7825; https://doi.org/10.3390/ijms21217825
Received: 21 September 2020 / Revised: 12 October 2020 / Accepted: 15 October 2020 / Published: 22 October 2020
(This article belongs to the Section Physical Chemistry and Chemical Physics)
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. View Full-Text
Keywords: bicycle-pedal isomerization; naphthopyran; photochromism; photodynamics; photophysics; quantum chemical calculations; reaction mechanisms; time-resolved spectroscopy bicycle-pedal isomerization; naphthopyran; photochromism; photodynamics; photophysics; quantum chemical calculations; reaction mechanisms; time-resolved spectroscopy
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MDPI and ACS Style

Brazevic, S.; Nizinski, S.; Sliwa, M.; Abe, J.; Rode, M.F.; Burdzinski, G. Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts. Int. J. Mol. Sci. 2020, 21, 7825. https://doi.org/10.3390/ijms21217825

AMA Style

Brazevic S, Nizinski S, Sliwa M, Abe J, Rode MF, Burdzinski G. Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts. International Journal of Molecular Sciences. 2020; 21(21):7825. https://doi.org/10.3390/ijms21217825

Chicago/Turabian Style

Brazevic, Sabina; Nizinski, Stanisław; Sliwa, Michel; Abe, Jiro; Rode, Michał F.; Burdzinski, Gotard. 2020. "Control of the Photo-Isomerization Mechanism in 3H-Naphthopyrans to Prevent Formation of Unwanted Long-Lived Photoproducts" Int. J. Mol. Sci. 21, no. 21: 7825. https://doi.org/10.3390/ijms21217825

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