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Mechanistic study of the trans,cis,cis-[RuCl2(DMSO)2(H2O)2] complex photochemistry in aqueous solutions

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Abstract

It is known that trans,cis,cis-[RuCl2(DMSO)2(H2O)2] (1a) complexes, which are formed upon dissolution of trans-[RuCl2(DMSO)4] in water, demonstrate light-induced cytotoxicity. The mechanistic study of 1a photochemistry has been performed using ultrafast pump–probe spectroscopy, laser flash photolysis and stationary photolysis. The first stage of 1a photochemistry is the photoexchange of a DMSO ligand to a water molecule; its quantum yield is wavelength-dependent (estimating by values 0.3 and 0.04 upon irradiation at 308 and 430 nm, respectively). The mechanism of photoexchange is complicated involving at least four Ru(ii) intermediates. Two tentative mechanisms of the process are proposed.

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Authors and Affiliations

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

    Anton A. Shushakov, Svetlana G. Matveeva, Ivan P. Pozdnyakov, Vjacheslav P. Grivin, Victor F. Plyusnin & Evgeni M. Glebov

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

    Anton A. Shushakov, Ivan P. Pozdnyakov, Vjacheslav P. Grivin, Victor F. Plyusnin, Danila B. Vasilchenko & Evgeni M. Glebov

  3. Nikolaev Institute of Inorganic Chemistry, 5 Lavrentyev Prosp., 630090, Novosibirsk, Russian Federation

    Danila B. Vasilchenko

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

    Alexei A. Melnikov & Sergei V. Chekalin

  5. Faculty of Physics, National Research University Higher School of Economics, 20 Myasnitskaya Str., 101000, Moscow, Russian Federation

    Alexei A. Melnikov

Authors
  1. Anton A. Shushakov
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  2. Svetlana G. Matveeva
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  3. Ivan P. Pozdnyakov
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  4. Vjacheslav P. Grivin
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  5. Victor F. Plyusnin
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  6. Danila B. Vasilchenko
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  7. Alexei A. Melnikov
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  8. Sergei V. Chekalin
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  9. Evgeni M. Glebov
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Corresponding author

Correspondence to Evgeni M. Glebov.

Additional information

Electronic supplementary information (ESI) available: Electronic absorption spectra of 1a and 2a, detailed pictures illustrating the changes in the UV-Vis spectra caused by dark and photochemical reactions, and part of laser flash photolysis data. See DOI: 10.1039/d0pp00178c

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Shushakov, A.A., Matveeva, S.G., Pozdnyakov, I.P. et al. Mechanistic study of the trans,cis,cis-[RuCl2(DMSO)2(H2O)2] complex photochemistry in aqueous solutions. Photochem Photobiol Sci 19, 1222–1229 (2020). https://doi.org/10.1039/d0pp00178c

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  • DOI: https://doi.org/10.1039/d0pp00178c

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