Photochemistry of hexachloroosmate(IV) in ethanol. Issue 11 (19th October 2020)

• Record Type: Journal Article
• Authors: Glebov, Evgeni M.; Matveeva, Svetlana G.; Pozdnyakov, Ivan P.; Grivin, Vjacheslav P.; Plyusnin, Victor F.; Vasilchenko, Danila B.; Romanova, Tamara E.; Melnikov, Alexei A.; Chekalin, Sergey V.; Fedunov, Roman G.
• Is Part Of: Photochemical & photobiological sciences. Volume 19:Issue 11(2020)
• Page Start: 1569
• Page End: 1579
• Publication Date: 2020-10-19
• Subjects: Photochemistry -- Periodicals; Photobiology -- Periodicals; 541.35
• DOI: 10.1039/d0pp00244e
• Languages: English
• ISSNs: 1474-905X

Abstract

Abstract : A mechanistic study of the Os IV Cl6 2− complex photochemistry in ethanol was performed. Abstract : The photochemistry of the Os IV Cl6 2− 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 Os IV Cl6 2− photochemistry.