Photochemistry of cis,trans-[PtIV(en)(I)2(CH3COO)2] complex in aqueous solutions
- Authors: Glebov E.M.1,2, Pozdnyakov I.P.1,2, Magin I.M.1, Grivin V.P.1,2, Plyusnin V.F.1,2, Vasil’chenko D.B.2,3, Zadesenets A.V.2,3, Mel’nikov A.A.4,5, Chekalin S.V.4
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Affiliations:
- V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences
- Novosibirsk State University
- A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences
- Institute of Spectroscopy, Russian Academy of Sciences
- Faculty of Physics, National Research University Higher School of Economics
- Issue: Vol 68, No 8 (2019)
- Pages: 1532-1541
- Section: Full Article
- URL: https://journals.rcsi.science/1066-5285/article/view/243449
- DOI: https://doi.org/10.1007/s11172-019-2588-y
- ID: 243449
Cite item
Abstract
The photochemistry of aqueous solutions of the cis,trans-[PtIV(en)(I)2(CH3COO)2] complex (1) was studied by stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy in the time interval from hundreds of femtoseconds to minutes. It is shown that the multistage photolysis, including photochemical reactions of ligand exchange and photoreduction, involves in the fi rst step the formation of the cis-[IV(en)(I)2(CH3COO)2] complex with a quantum yield of 0.3 (irradiation at 282 nm). The further ligand exchange and photoreduction reactions occur with much lower quantum yields. The photochemical exchange of the acetate ion occurs in a time interval of ~100 ps with the much slower final step, being probably the acidic dissociation of the product. The key intermediate of the first step of the process was detected in the picosecond time range. Depending on the interpretation of the key intermediate nature, two possible mechanisms of the primary photochemical process are proposed.
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
I. M. Magin
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
V. P. Grivin
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. 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
D. B. Vasil’chenko
Novosibirsk State University; A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 2 ul. Pirogova, Novosibirsk, 630090; 3 prosp. Lavrent’eva, Novosibirsk, 630090
A. V. Zadesenets
Novosibirsk State University; A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 2 ul. Pirogova, Novosibirsk, 630090; 3 prosp. Lavrent’eva, Novosibirsk, 630090
A. A. Mel’nikov
Institute of Spectroscopy, Russian Academy of Sciences; Faculty of Physics, National Research University Higher School of Economics
Email: glebov@kinetics.nsc.ru
Russian Federation, 5 ul. Fizicheskaya, Troitsk, Moscow, 142190; 20 ul. Myasnitskaya, Moscow, 101000
S. V. Chekalin
Institute of Spectroscopy, Russian Academy of Sciences
Email: glebov@kinetics.nsc.ru
Russian Federation, 5 ul. Fizicheskaya, Troitsk, Moscow, 142190