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Comparison of the Photochemistry of Acyclic and Cyclic 4-(4-Methoxy-phenyl)-4-oxo-but-2-enoate Ester Derivatives

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2020, 124, 37, 7346-7354
    A: Kinetics, Dynamics, Photochemistry, and Excited States

    Comparison of the Photochemistry of Acyclic and Cyclic 4-(4-Methoxy-phenyl)-4-oxo-but-2-enoate Ester Derivatives
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    • Sujan K. Sarkar
      Sujan K. Sarkar
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
      More by Sujan K. Sarkar
      Orcidhttp://orcid.org/0000-0002-8471-6297
    • Ranaweera A. A. Upul Ranaweera
      Ranaweera A. A. Upul Ranaweera
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
      More by Ranaweera A. A. Upul Ranaweera
      Orcidhttp://orcid.org/0000-0003-1614-1919
    • Rajkumar Merugu
      Rajkumar Merugu
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
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    • Nayera M. Abdelaziz
      Nayera M. Abdelaziz
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
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    • Jendai Robinson
      Jendai Robinson
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
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    • Heidi A. Day
      Heidi A. Day
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
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    • Jeanette A. Krause
      Jeanette A. Krause
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
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    • Anna D. Gudmundsdottir*
      Anna D. Gudmundsdottir
      Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
      *Email: [email protected]. Phone: 513-556-3380.
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      Orcidhttp://orcid.org/0000-0002-5420-4098
    Other Access OptionsSupporting Information (2)

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2020, 124, 37, 7346–7354
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.0c04319
    Published August 5, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    To clarify the cis–trans isomerization mechanism of simple alkenes on the triplet excited state surface, the photochemistry of acyclic and cyclic vinyl ketones with a p-methoxyacetophenone moiety as a built-in triplet sensitizer (1 and 2, respectively) was compared. When irradiated, ketone 1 produces its cis-isomer, whereas ketone 2 does not yield any photoproducts. Laser flash photolysis of ketone 1 yields a transient spectrum with λmax ∼ 400 nm (τ ∼ 125 ns). This transient is assigned to the first triplet excited state (T1) of 1, which presumably decays to form a triplet biradical (1BR) that is shorter lived than the triplet ketone. In comparison, laser flash photolysis of 2 reveals two transients (τ ∼ 20 and 440 ns), which are assigned to T1 of 2 and triplet biradical 2BR, respectively. Density functional theory calculations support the characterization of the triplet excited states and the biradical intermediates formed upon irradiation of ketones 1 and 2 and allow a comparison of the physical properties of the biradical intermediates. As the biradical centers in 2BR are stabilized by conjugation, 2BR is more rigid than 1BR. Therefore, the longer lifetime of 2BR can be attributed to less-efficient intersystem crossing to the ground state.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c04319.

    • NMR and IR spectra of 1 and 2; Cartesian coordinates and energies of 1, 2, T1 of 1, T1 of 2, 1BR, and 2BR (PDF)

    • Crystallographic details for 2 (CIF)

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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2020, 124, 37, 7346–7354
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.0c04319
    Published August 5, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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