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    Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

    Access Status
    Fulltext not available
    Authors
    Sneeden, E.
    Hackett, Mark
    Cotelesage, J.
    Prince, R.
    Barney, M.
    Goto, K.
    Block, E.
    Pickering, I.
    George, G.
    Date
    2017
    Type
    Journal Article
    
    Metadata
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    Citation
    Sneeden, E. and Hackett, M. and Cotelesage, J. and Prince, R. and Barney, M. and Goto, K. and Block, E. et al. 2017. Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy. Journal of the American Chemical Society. 139 (33): pp. 11519-11526.
    Source Title
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.7b05116
    ISSN
    0002-7863
    School
    Department of Chemistry
    URI
    http://hdl.handle.net/20.500.11937/57066
    Collection
    • Curtin Research Publications
    Abstract

    Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s?3p transition to the singly occupied molecular orbital of the free radical. Our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.

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