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Tailored Nitroxide Radicals and Biradical Containing 13C Enriched Acetylene Groups: ENDOR and DFT Investigation

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Abstract

A specially synthesized nitroxide biradical R5-C≡13C-(p-C6H4)2-13C≡C-R5 (B4) and two radicals, R5-C≡13CH (RCC) and R5-C≡13C-C6H5 (RCCPh), where R5 is 1-oxyl-2,2,5,5-tetramethyl-pyrroline group, have been studied by X- and W-band electron paramagnetic resonance (EPR) spectroscopy, and by W-band electron-nuclear double resonance (ENDOR). Spin density distribution and hyperfine splitting (hfs) constants on 13C atoms were experimentally determined and also calculated using ORCA 3.0.3 program package. The biradical and radicals geometries were optimized on UKS/B3LYP/cc-pVDZ level. Hfs constants were calculated using density functional theory (DFT) with PBE0 functional and N07D, and were compared with the experimental value of the hfs constant on 13C atoms, measured from ENDOR spectra. It is concluded that at small values of the exchange integral as J ≤ a/2 ≈ 7–8 G, the current quantum chemical approaches do not allow determining precise values of the hfs constants on the 13C atoms in the bridge connecting two paramagnetic nitroxide rings of the biradical.

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Acknowledgements

This work was supported by the Grants GINOP 2.3.2-15-2016-00049 and GINOP-2.3.2-15-2016-00025. The present scientific contribution is dedicated to the 650th anniversary of the foundation of the University of Pécs, Hungary. The study was also supported by the Supercomputing Center of M. V. Lomonosov Moscow State University [49], and through the Program of Fundamental Research of the Presidium of the Russian Academy of Sciences (no. 1.26П). AIK also thanks 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.

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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

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

    R. B. Zaripov

  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, Szigeti st. 12, Pécs, 7624, Hungary

    K. Hideg & T. Kálai

  5. Szentágothai Research Center, Ifjúság st. 20, Pécs, 7624, Hungary

    T. Kálai

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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. K. Hideg
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  5. T. Kálai
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Correspondence to A. I. Kokorin.

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Kokorin, A.I., Zaripov, R.B., Gromov, O.I. et al. Tailored Nitroxide Radicals and Biradical Containing 13C Enriched Acetylene Groups: ENDOR and DFT Investigation. Appl Magn Reson 49, 137–149 (2018). https://doi.org/10.1007/s00723-017-0942-5

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  • DOI: https://doi.org/10.1007/s00723-017-0942-5

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