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Generation of Long-Lived Phenoxyl Radical in the Binuclear Copper(II) Pivalate Complex with 2,6-Di-tert-butyl-4-(3,5-bis(4-pyridyl)pyridyl)phenol

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Abstract

A new binuclear copper(II) complex Cu2(Piv)4(L)2, where Piv– = pivalate, L = 2,6-di-tert-butyl-4-(3,5-bis(4-pyridyl)pyridyl)phenol, was synthesized, and its molecular and crysral structures were determined at temperatures of 160, 173, and 296 K (CIF files CCDC no. 2144104, 2144105, and 2144106, respectively). Cyclic voltammetry measurements revealed three irreversible oxidation processes in the potential range of 0.5–1.2 V versus Fc+/Fc. Analysis of the temperature dependence of the magnetic susceptibility of Cu2(Piv)4(L)2 showed that antiferromagnetic interactions of Cu2+ ions predominate in the complex. It was found that the oxidation of Cu2(Piv)4(L)2 upon grinding with PbO2 or treatment of a solid sample with an aqueous solution of K3[Fe(CN)6] affords long-lived phenoxyl radical, which can be detected by ESR spectroscopy.

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ACKNOWLEDGMENTS

A.V. Pavlishchuk, V.V. Pavlishchuk, V.N. Dorofeeva, S.V. Kolotilov, and K.S. Gavrilenko are grateful to the National Academy of Sciences of Ukraine (Project “Metal-Organic Frameworks and Polynuclear Complexes: Chemical Design, Structural Adsorption and Magnetic Luminescent Properties” based on the results of the joint competition of the National Academy of Sciences of Ukraine and the Russian Foundation for Basic Research of 2012). M.A. Kiskin, N.N. Efimov, V.V. Minin, and I.L. Eremenko are grateful to the Ministry of Education and Science of the Russian Federation for funding the research carried out within the framework of the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences. The authors wish to thank A.S. Litvinenko (Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine) for help in cyclic voltammogram measurements.

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Authors and Affiliations

  1. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Kyiv, Ukraine

    V. N. Dorofeeva, A. V. Pavlishchuk, S. V. Kolotilov & V. V. Pavlishchuk

  2. Taras Shevchenko National University of Kyiv, Kyiv, Ukraine

    A. V. Pavlishchuk & K. S. Gavrilenko

  3. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia

    M. A. Kiskin, N. N. Efimov, V. V. Minin & I. L. Eremenko

  4. Enamine Research and Production Association, Kyiv, Ukraine

    K. S. Gavrilenko

  5. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

    I. L. Eremenko

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  1. V. N. Dorofeeva
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  2. A. V. Pavlishchuk
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  3. M. A. Kiskin
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  4. N. N. Efimov
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  6. K. S. Gavrilenko
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  7. S. V. Kolotilov
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  8. V. V. Pavlishchuk
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Correspondence to M. A. Kiskin.

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The authors congratulate Academician V. I. Ovcharenko on the 70th birthday

Translated by Z. Svitanko

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Dorofeeva, V.N., Pavlishchuk, A.V., Kiskin, M.A. et al. Generation of Long-Lived Phenoxyl Radical in the Binuclear Copper(II) Pivalate Complex with 2,6-Di-tert-butyl-4-(3,5-bis(4-pyridyl)pyridyl)phenol. Russ J Coord Chem 48, 422–429 (2022). https://doi.org/10.1134/S1070328422070041

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