Issue 1, 2018

Short-lived intermediates in photochemistry of an OsCl62− complex in aqueous solutions

Abstract

Two mechanisms of OsIVCl62− photolysis were studied by means of quantum chemical calculations in gas and aqueous phases. The difference between these mechanisms is in the nature of the possible Os(IV) key intermediates (KI). According to calculations, the intermediate is an OsIVCl5 complex of square pyramidal coordination geometry. The calculations do not give an opportunity to make an unambiguous choice between the triplet and quintet multiplicities of OsIVCl5. The calculated CASSCF/IMCP-SR1 transition energies for 5OsIVCl5 are lower than for 3OsIVCl5, while the calculated XMC-QDPT2/SBKJC spectra for the triplet state are in better agreement with the experimental absorption spectrum of the KI than for the quintet state.

Graphical abstract: Short-lived intermediates in photochemistry of an OsCl62− complex in aqueous solutions

Supplementary files

Article information

Article type
Paper
Submitted
10 Aug 2017
Accepted
01 Nov 2017
First published
02 Nov 2017
This article is Open Access
Creative Commons BY license

Photochem. Photobiol. Sci., 2018,17, 18-26

Short-lived intermediates in photochemistry of an OsCl62− complex in aqueous solutions

M. V. Rogozina, V. V. Yudanov, R. G. Fedunov, I. P. Pozdnyakov, A. A. Melnikov, S. V. Chekalin and E. M. Glebov, Photochem. Photobiol. Sci., 2018, 17, 18 DOI: 10.1039/C7PP00299H

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