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Probing Photochemically and Thermally Induced Isomerization Reactions in α-Pyrone

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)7249-7254
Number of pages6
JournalJournal of Physical Chemistry A
Volume120
Journal issue37
Early online date1 Sep 2016
DOIs
StatePublished - 22 Sep 2016

Abstract

The isomerization dynamics of α-pyrone dissolved in CH3CN have been probed by femtosecond 267 nm pump/broadband infrared (IR) probe spectroscopy. A novel experimental setup allowed the populations of the parent molecule and ring-opened photoproducts to be monitored over pump/probe time delays ranging between 2 ps and 100 μs within a single experiment, and at 5 different temperatures between 0 and 40 °C. The photochemically prepared α-pyrone(S1) molecules decay rapidly (0 potential energy surface, with an initial quantum yield for parent molecule re-formation of 60%. Probing the antisymmetric ketene stretch region (2100-2150 cm-1) confirms the presence of at least two ring-opened photoproducts, which are assumed to have an E-configuration with respect to the central C=C double bond. These ketenes are observed to undergo two distinct, thermally driven, isomerization processes which occur on the nanosecond and microsecond time scales, respectively. The former reaction is ascribed to thermalization of the initially prepared E-isomer populations, while the slower (microsecond) process involves rotation around the central C=C double bond leading to formation of Z-isomers. Subsequent rapid Z → Z isomerizations (occurring on a nanosecond time scale) result in ring-closure and a second, longer time recovery of parent molecule population. By determining rates as a function of the sample temperature, barrier heights of 0.23(3) eV and 0.43(2) eV are obtained for the E → E and E → Z transformations, respectively.

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    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via ACS at http://pubs.acs.org/doi/abs/10.1021/acs.jpca.6b06396. Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 775 KB, PDF-document

    License: CC BY-NC

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