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The Structure and EPR Behavior of Nitroxide Biradical Containing Phosphorus Atom in the Bridge

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Abstract

Two short nitroxide biradicals of similar composition: (H5C6)O=P(OR6)2 (BP) and O=S(OR6)2 (BS), where OR6 is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, have been studied by electron paramagnetic resonance spectroscopy, and X-ray structural analysis. Variations of the intramolecular electron spin exchange in the biradicals, dissolved in toluene, as a function of temperature were characterized by changes in the isotropic 14N hyperfine splitting (hfs) constant a, values of the exchange integral |J|, and compared with the X-ray structural data. Thermodynamic parameters of the conformational rearrangements were calculated. Geometry optimization and spin density distribution calculations of biradical BP were carried out on the DFT/UB3LYPPBE0/cc-pVdTZz and DFT/ROPBE/N07D levels of theory and compared with those of BS. Probable differences in biradicals behavior are discussed.

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Acknowledgments

This work was financially supported by the Russian Foundation for Basic Research (project no. 12-03-00623-a). AIK and OIG are grateful to Dr. E.N. Golubeva (Chemistry Department, M.V. Lomonosov Moscow State University) for helpful discussions, and to Dr. A.A. Shubin (G.K. Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences), who kindly provided us with his program package.

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Authors and Affiliations

  1. N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation

    Alexander I. Kokorin & Oleg I. Gromov

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russian Federation

    Victor N. Khrustalev

  3. Peoples’ Friendship University of Russia, Miklukho-Maklay Street, 6, 117198, Moscow, Russian Federation

    Victor N. Khrustalev

  4. Chemistry Department, M. Lomonosov Moscow State University, Moscow, Russian Federation

    Oleg I. Gromov

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  1. Alexander I. Kokorin
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  2. Victor N. Khrustalev
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  3. Oleg I. Gromov
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Correspondence to Alexander I. Kokorin.

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Kokorin, A.I., Khrustalev, V.N. & Gromov, O.I. The Structure and EPR Behavior of Nitroxide Biradical Containing Phosphorus Atom in the Bridge. Appl Magn Reson 46, 1429–1442 (2015). https://doi.org/10.1007/s00723-015-0716-x

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