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Detection of the Photoreversibility of NO2-ONO Linkage Isomerization in [Co(NH3)5NO2]Cl(NO3) Crystals by the Photomechanical Response Method

  • KINETICS AND MECHANISM OF CHEMICAL REACTIONS, CATALYSIS
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Abstract

The linkage isomerization of NO2-ONO (nitro-nitrito) in the complex cation [Co(NH3)5NO2]2+ is a well-studied classical reaction. It is believed that the photoisomerization of the nitro form to the nitrito form in the crystalline phase reaches complete transformation at a low temperature, while the reverse transformation proceeds as a first-order thermal intramolecular reaction upon the heating of the crystals. To date, there is no information on the possibility of reverse photoisomerization. In this study, photoisomerization in [Co(NH3)5NO2]Cl(NO3) crystals is investigated by the analysis of the crystal deformation caused by the transformation under irradiation at different wavelengths. A change in the lattice parameters during the transformation leads to reliably measurable elongation and bending of acicular crystals. It is shown that the limiting elongation of the crystal under prolonged irradiation depends on the wavelength, which proves the reversibility of photoisomerization. The quantum yield of the reverse reaction is estimated to be 0.04 of the quantum yield of the direct reaction.

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Funding

This study was supported by the Russian Science Foundation, grant no. 22-23-01130.

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Authors and Affiliations

  1. Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    S. A. Chizhik, P. A. Gribov, V. Yu. Kovalskii & A. A. Sidelnikov

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  1. S. A. Chizhik
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  2. P. A. Gribov
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  3. V. Yu. Kovalskii
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  4. A. A. Sidelnikov
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Correspondence to S. A. Chizhik.

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ADDITIONAL INFORMATION

This article is part of the Materials of the X International Voevodsky Conference “Physics and Chemistry of Elementary Chemical Processes” (September 2022, Novosibirsk, Russia).

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Chizhik, S.A., Gribov, P.A., Kovalskii, V.Y. et al. Detection of the Photoreversibility of NO2-ONO Linkage Isomerization in [Co(NH3)5NO2]Cl(NO3) Crystals by the Photomechanical Response Method. Russ. J. Phys. Chem. B 18, 153–165 (2024). https://doi.org/10.1134/S1990793124010226

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