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Influence of Pressure on the Intramolecular Spin Exchange in a Short Imidazolium-Nitroxide Biradical

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Abstract

A short-chain imidazoline-type nitroxide biradical R NO5 –CH=N–N=C(CH3)–R N5 , B2, with nitroxide rings R N5 and R NO5 as 1-oxyl-2,2,5,5-tetramethyl-3-imidazoline and 1-oxyl-2,2,5,5-tetramethyl-3-N-oxide imidazoline, respectively, has been studied using X-band electron paramagnetic resonance (EPR) spectroscopy in CH3CN solutions at variable temperature T and pressure P. Changes of the solution viscosity on the intramolecular electron spin exchange in B2 is characterized by calculating the value of the exchange integral |J/a|, where a denotes the 14N hyperfine splitting (hfs) constant. It is revealed that the intramolecular dynamics in B2 do not follow the Debye–Stokes–Einstein law, while the Arrhenius dependence is fulfilled. Probable reasons of such behavior are discussed.

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Acknowledgements

We are grateful to Prof. Dr. I. A. Grigor’ev (Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB RAS, Novosibirsk) who presented us with a sample of the biradical, and to Dr. A. A. Shubin (Boreskov Institute of Catalysis, SB RAS, Novosibirsk) who kindly provided us his program package.

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Authors and Affiliations

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

    Boryana Mladenova-Kattnig & Günter Grampp

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

    Alexander I. Kokorin

Authors
  1. Boryana Mladenova-Kattnig
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  2. Günter Grampp
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  3. Alexander I. Kokorin
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Correspondence to Alexander I. Kokorin.

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Mladenova-Kattnig, B., Grampp, G. & Kokorin, A.I. Influence of Pressure on the Intramolecular Spin Exchange in a Short Imidazolium-Nitroxide Biradical. Appl Magn Reson 48, 327–334 (2017). https://doi.org/10.1007/s00723-017-0865-1

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  • DOI: https://doi.org/10.1007/s00723-017-0865-1

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