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Peculiarities of Spin Exchange in Nitroxide Biradicals Containing Two para-Phenylene Groups in the Bridge: EPR Investigation and DFT Calculations

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Abstract

Two nitroxide biradicals of similar composition: R5-C≡C-Ph-Ph-C≡C-R5 (B3a) and R6-C≡C-Ph-Ph-C≡C-R6 (B3b), where Ph = p-C6H4, and R6 is 2,6,6-tetramethyl-5,6-dihydropyridin-1(2H)-yloxyl, and R5 is 2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-1-yloxyl nitroxide rings, have been studied by electron paramagnetic resonance (EPR) spectroscopy. 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 data obtained by density functional theory calculations (DFT). Thermodynamic parameters of the conformational rearrangements were calculated. Geometries of nitroxide biradicals in PES local minima and transition states in the triplet state were calculated at UDFT/B3LYP level with split-valence basis set cc-PVTZ. Probable differences in biradicals behavior are discussed.

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Acknowledgments

This work was financially supported by National Research Development and Innovation Office, Hungary (OTKA104956). Authors are grateful to Prof. E. N. Golubeva (M. V. Lomonosov Moscow State University, Chemistry Department) for useful comments and to Dr. A. A. Shubin (Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk) who provided us with his computer program package of EPR spectra simulation. DFT calculations were performed using resources of the Supercomputing Center of M. V. Lomonosov Moscow State University [41].

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

    Oleg I. Gromov

  3. Institute of Organic and Medical Chemistry, University of Pécs, Pécs, Hungary

    Tamás Kálai & Kálmán Hideg

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  1. Alexander I. Kokorin
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  2. Oleg I. Gromov
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  3. Tamás Kálai
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  4. Kálmán Hideg
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Correspondence to Alexander I. Kokorin.

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Kokorin, A.I., Gromov, O.I., Kálai, T. et al. Peculiarities of Spin Exchange in Nitroxide Biradicals Containing Two para-Phenylene Groups in the Bridge: EPR Investigation and DFT Calculations. Appl Magn Reson 47, 1283–1293 (2016). https://doi.org/10.1007/s00723-016-0826-0

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