期刊
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
卷 21, 期 21, 页码 -出版社
MDPI
DOI: 10.3390/ijms21217825
关键词
bicycle-pedal isomerization; naphthopyran; photochromism; photodynamics; photophysics; quantum chemical calculations; reaction mechanisms; time-resolved spectroscopy
资金
- National Science Centre (NCN), Poland [2017/27/B/ST4/00320]
- CNRS IRP Nano-synergetics
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 S-1 -> S-0 internal conversion populating back the TC species in the ground electronic state. This is validated by a shorter TC S-1 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.
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