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Features of spin exchange in nitroxide biradicals in the ionic liquid bmimPF6

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Abstract

The intramolecular electron spin exchange has been studied by electron paramagnetic resonance (EPR) spectroscopy in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) for various nitroxide biradicals as a function of temperature and the nature of the connecting bridge between two >NO· centers. Temperature variations of the isotropic nitrogen hyperfine splitting constant a and exchange integral values |J/a| were measured from EPR spectra and analyzed. Thermodynamic parameters of the conformational rearrangements were obtained. The spin exchange in rigid and flexible biradicals dissolved in the ionic liquid bmimPF6 was compared with that in toluene solutions. Interesting features of the spin exchange in biradicals in ionic liquid were observed and explained as a result of the specific intramolecular conformational transitions. The first example of a rather rigid biradical molecule becoming flexible under the influence of an ionic liquid is reported.

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Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Graz University of Technology, Graz, Austria

    V. A. Tran, G. Grampp & K. Rasmussen

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

    Aleksandr I. Kokorin

  3. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina 4, 119991, Moscow, Russian Federation

    Aleksandr I. Kokorin

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  1. V. A. Tran
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  2. Aleksandr I. Kokorin
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  3. G. Grampp
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  4. K. Rasmussen
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Correspondence to Aleksandr I. Kokorin.

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Tran, V.A., Kokorin, A.I., Grampp, G. et al. Features of spin exchange in nitroxide biradicals in the ionic liquid bmimPF6 . Appl Magn Reson 35, 389–398 (2009). https://doi.org/10.1007/s00723-009-0170-8

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  • DOI: https://doi.org/10.1007/s00723-009-0170-8

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