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Photochemistry of hexachloroosmate(IV) in ethanol

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Abstract

The photochemistry of the OsIVCl62− complex in ethanol was studied by means of stationary photolysis, nanosecond laser flash photolysis, ultrafast pump-probe spectroscopy and quantum chemistry. The direction of the photochemical process was found to be wavelength-dependent. Irradiation in the region of the d-d and LMCT bands results in the photosolvation (with the wavelength-dependent quantum yield) and photoreduction of Os(iv) to Os(iii), correspondingly. The characteristic time of photosolvation is ca. 40 ps. Photoreduction occurs in the micro- and millisecond time domains via several Os(iii) intermediates. The nature of intermediates and the possible mechanisms of photoreduction are discussed. We believe that the lability of the photochemically produced Os(iv) and Os(iii) intermediates determines the synthetic potential of OsIVCl62− photochemistry.

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Authors and Affiliations

  1. V.V. Voevodsky Institute of Chemical Kinetics and Combustion, 3 Institutskaya Str., 630090, Novosibirsk, Russian Federation

    Evgeni M. Glebov, Svetlana G. Matveeva, Ivan P. Pozdnyakov, Vjacheslav P. Grivin, Victor F. Plyusnin & Roman G. Fedunov

  2. Novosibirsk State University, 2 Pirogova Str., 630090, Novosibirsk, Russian Federation

    Evgeni M. Glebov, Ivan P. Pozdnyakov, Vjacheslav P. Grivin, Victor F. Plyusnin, Danila B. Vasilchenko & Tamara E. Romanova

  3. A.V. Nikolaev Institute of Inorganic Chemistry, 3 Lavrentyev Ave., 630090, Novosibirsk, Russian Federation

    Danila B. Vasilchenko & Tamara E. Romanova

  4. Institute of Spectroscopy, 5 Fizicheskaya Str., 119333, Troitsk, Moscow, Russian Federation

    Alexei A. Melnikov & Sergey V. Chekalin

  5. Faculty of Physics, 20 Myasnitskaya Str., 101000, Moscow, Russian Federation

    Alexei A. Melnikov

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  1. Evgeni M. Glebov
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  2. Svetlana G. Matveeva
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Correspondence to Evgeni M. Glebov.

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Glebov, E.M., Matveeva, S.G., Pozdnyakov, I.P. et al. Photochemistry of hexachloroosmate(IV) in ethanol. Photochem Photobiol Sci 19, 1569–1579 (2020). https://doi.org/10.1039/d0pp00244e

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