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Unexpected Features of the Intramolecular Spin Exchange in Imidazoline Nitroxide Biradicals Dissolved in Ionic Liquids

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Abstract

Three imidazoline-type nitroxide biradicals of the similar composition R NO5 –CH=N–N=CH–R N5 , B1, R NO5 –CH=N–N=C(CH3)–R N5 , B2, and R N5 –C(CH3)=N–N=C(CH3)–R N5 , B3, with R N5 and R NO5 denoting, respectively, the nitroxide rings 1-oxyl-2,2,5,5-tetramethyl-3-imidazoline and 1-oxyl-2,2,5,5-tetramethyl-3-N–oxide imidazoline, have been studied by X-band electron paramagnetic resonance (EPR) spectroscopy. Variations of the intramolecular electron spin exchange in these biradicals dissolved in ethanol and the room temperature ionic liquid bmimBF4 were characterized as a function of temperature by means of the analysis of the EPR lines shape. Thermodynamic parameters of the conformational rearrangements in ethanol were calculated. Analyzing the EPR spectra of these biradicals in bmimBF4, it was revealed that the two-conformational model does not describe their conformational transitions. Moreover, the observed EPR spectra are not central symmetric especially at low temperatures that cannot be described and explained in the framework of the current theory of the intramolecular spin exchange. Probable reasons of this “strange” behavior are discussed.

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Acknowledgements

We are grateful to Dr. A. A. Shubin (Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk) who provided us 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. Institute of Physical and Theoretical Chemistry, Graz University of Technology, Graz, Austria

    B. Y. Mladenova-Kattnig & G. Grampp

  3. Novosibirsk Institute of Organic Chemistry SB RAS, Novosibirsk, Russian Federation

    I. A. Grigor’ev

Authors
  1. A. I. Kokorin
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  2. B. Y. Mladenova-Kattnig
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  3. I. A. Grigor’ev
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  4. G. Grampp
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Correspondence to A. I. Kokorin.

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Kokorin, A.I., Mladenova-Kattnig, B.Y., Grigor’ev, I.A. et al. Unexpected Features of the Intramolecular Spin Exchange in Imidazoline Nitroxide Biradicals Dissolved in Ionic Liquids. Appl Magn Reson 48, 287–296 (2017). https://doi.org/10.1007/s00723-016-0858-5

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  • DOI: https://doi.org/10.1007/s00723-016-0858-5

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