Primary photophysical and photochemical processes for Pt(SCN)62– complex
- Authors: Glebov E.M.1,2, Pozdnyakov I.P.1,2, Chernetsov V.P.3, Grivin V.P.1, Venediktov A.B.4, Melnikov A.A.5, Chekalin S.V.5, Plyusnin V.F.1,2
-
Affiliations:
- V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences
- Novosibirsk State University
- Novosibirsk State Technical University
- A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences
- Institute of Spectroscopy, Russian Academy of Sciences
- Issue: Vol 66, No 3 (2017)
- Pages: 418-425
- Section: Full Articles
- URL: https://journals.rcsi.science/1066-5285/article/view/240125
- DOI: https://doi.org/10.1007/s11172-017-1749-0
- ID: 240125
Cite item
Abstract
Photosolvation of a PtIV hexathiocyanate complex Pt(SCN)62– in water and ethanol was studied by steady-state photolysis, nanosecond laser flash photolysis, and ultrafast kinetic spectroscopy. Complexes Pt(SCN)5(H2O)– and Pt(SCN)5(C2H5OH)– were found to be the only reaction products. The quantum yields of photosolvation are independent of the excitation wavelength, being equal to 0.25 and 0.5 for the solutions of the complex in water and ethanol, respectively. Photosolvation proceeds by the mechanism of heterolytic metal—ligand bond dissociation without involvement of redox processes. The characteristic time of formation of the end products for both solvents is about 10 ps. Three successive intermediates detected on the picosecond time scale were interpreted as PtIV complexes. The nature of the intermediates and possible mechanisms of photosolvation are discussed.
About the authors
E. M. Glebov
V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences; Novosibirsk State University
Author for correspondence.
Email: glebov@kinetics.nsc.ru
Russian Federation, 3 ul. Institutskaya, Novosibirsk, 630090; 2 ul. Pirogova, Novosibirsk, 630090
I. P. Pozdnyakov
V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences; Novosibirsk State University
Email: glebov@kinetics.nsc.ru
Russian Federation, 3 ul. Institutskaya, Novosibirsk, 630090; 2 ul. Pirogova, Novosibirsk, 630090
V. P. Chernetsov
Novosibirsk State Technical University
Email: glebov@kinetics.nsc.ru
Russian Federation, 20 prosp. Karla Marksa, Novosibirsk, 630073
V. P. Grivin
V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 3 ul. Institutskaya, Novosibirsk, 630090
A. B. Venediktov
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 5 prosp. Lavrent’eva, Novosibirsk, 630090
A. A. Melnikov
Institute of Spectroscopy, Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 5 ul. Fizicheskaya, Troitsk, Moscow, 142190
S. V. Chekalin
Institute of Spectroscopy, Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 5 ul. Fizicheskaya, Troitsk, Moscow, 142190
V. F. Plyusnin
V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences; Novosibirsk State University
Email: glebov@kinetics.nsc.ru
Russian Federation, 3 ul. Institutskaya, Novosibirsk, 630090; 2 ul. Pirogova, Novosibirsk, 630090