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Spin Density Distribution in a Nitroxide Biradical Containing 13C-Enriched Acetylene Groups in the Bridge: DFT Calculations and EPR Investigation

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Abstract

A specially synthesized nitroxide biradical R6-13C≡C-p-C6H4–C≡13C-R6, B3, where R6 = 1-oxyl-2,2,6,6-tetramethyl-1,2,3,6-tetrahydropyridine nitroxide, has been studied by electron paramagnetic resonance spectroscopy, and electron-nuclear double resonance (ENDOR). Spin density distribution and hyperfine splitting (hfs) constant on 13C atoms calculations for biradical B3 were carried out using B3LYP and PBE0 functionals and several different basis sets including N07 family and were compared with the experimental value of the hfs constant on 13C atoms, measured from ENDOR spectra of B3. The mechanism of the intramolecular electron spin exchange in B3 biradical is discussed.

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Acknowledgments

This research was partly supported by Hungarian National, Research, Development and Innovation Office (OTKA104956). The study was also supported by the Supercomputing Center of M. V. Lomonosov Moscow State University [47]. 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

    A. I. Kokorin & O. I. Gromov

  2. Zavoisky Kazan Physical-Technical Institute, Russian Academy of Sciences, Kazan, Russian Federation

    R. B. Zaripov & A. A. Sukhanov

  3. Chemistry Department, M. V. Lomonosov Moscow State University, Moscow, Russian Federation

    O. I. Gromov

  4. Institute of Organic and Medicinal Chemistry, University of Pécs, PO Box 99, Pecs, 7602, Hungary

    T. Kálai, É. Lamperth & K. Hideg

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  1. A. I. Kokorin
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  2. R. B. Zaripov
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  3. O. I. Gromov
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  4. A. A. Sukhanov
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  5. T. Kálai
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  7. K. Hideg
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Correspondence to A. I. Kokorin.

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Kokorin, A.I., Zaripov, R.B., Gromov, O.I. et al. Spin Density Distribution in a Nitroxide Biradical Containing 13C-Enriched Acetylene Groups in the Bridge: DFT Calculations and EPR Investigation. Appl Magn Reson 47, 1057–1067 (2016). https://doi.org/10.1007/s00723-016-0813-5

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  • DOI: https://doi.org/10.1007/s00723-016-0813-5

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