Photochemistry of hexachloroosmate(IV) in ethanol

Evgeni M. Glebov, Svetlana G. Matveeva, Ivan P. Pozdnyakov, Vjacheslav P. Grivin, Victor F. Plyusnin, Danila B. Vasilchenko, Tamara E. Romanova, Alexei A. Melnikov, Sergey V. Chekalin, Roman G. Fedunov

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)1569-1579
Number of pages11
JournalPhotochemical and Photobiological Sciences
Volume19
Issue number11
DOIs
Publication statusPublished - Nov 2020

Keywords

  • ELECTRON-TRANSFER SPECTRA
  • LASER FLASH-PHOTOLYSIS
  • OSCL62-COMPLEX
  • WATER

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