Skip to main content
SpringerLink
Log in

Features of Spin Exchange in Short-Chain Nitroxide Biradicals in Ionic Liquids

  • Published:
Applied Magnetic Resonance Aims and scope Submit manuscript

Abstract

The intramolecular electron spin exchange has been studied by electron paramagnetic resonance (EPR) spectroscopy in the room temperature ionic liquids (RTIL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) and 1-octyl-3-methylimidazolium tetrafluoroborate (omimBF4) for three nitroxide biradicals with analogous structures of the connecting bridge between two >N–O· centers as a function of temperature. Temperature variations of the isotropic nitrogen hyperfine splitting constant a, and exchange integral values |J/a| were determined from EPR spectra and analyzed. Thermodynamic parameters of the conformational rearrangements were obtained. The spin exchange in rather rigid short-chain biradicals dissolved in omimBF4 and bmimPF6 was compared with that in toluene solutions. Interesting features of the spin exchange in biradicals in RTIL were observed and explained as a result of the specific intramolecular conformational transitions. Examples when rather rigid biradical molecules become flexible under an influence of RTIL are reported.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. E.G. Rozantsev, Free Nitroxyl Radicals (Plenum Press, New York, 1970)

    Google Scholar 

  2. A.L. Buchachenko, A.M. Wasserman, Stable Radicals (Khimiya, Moscow, 1973)

    Google Scholar 

  3. G.R. Luckharst, in Spin Labeling. Theory and Applications, ed. by L.J. Berliner (Academic Press, New York, 1976), pp. 133–181

  4. V.N. Parmon, A.I. Kokorin, G.M. Zhidomirov, Russ. J. Struct. Chem. 18, 104 (1977)

    Article  Google Scholar 

  5. V.N. Parmon, A.I. Kokorin, G.M. Zhidomirov, Stable Biradicals (Nauka, Moscow, 1980)

    Google Scholar 

  6. I.A. Grigor’ev, S.A. Dikanov, in Imidazoline Nitroxides. Synthesis, Properties, Applications, vol. 1, ed. by L.B. Volodarsky (CRC Press, Boca Raton, 1988), pp. 77–150

  7. G.R. Eaton, S.S. Eaton, Acc. Chem. Res. 21, 107 (1988)

    Article  Google Scholar 

  8. A.I. Kokorin, Appl. Magn. Reson. 26, 253 (2004)

    Article  Google Scholar 

  9. G. Grampp, K. Rasmussen, A.I. Kokorin, Appl. Magn. Reson. 26, 245 (2004)

    Article  Google Scholar 

  10. A.I. Kokorin, V.A. Tran, K. Rasmussen, G. Grampp, Appl. Magn. Reson. 30, 40 (2006)

    Article  Google Scholar 

  11. V.A. Tran, K. Rasmussen, G. Grampp, A.I. Kokorin, Appl. Magn. Reson. 32, 395 (2007)

    Article  Google Scholar 

  12. E.K. Metzner, L.J. Libertini, M. Calvin, J. Am. Chem. Soc. 96, 6515 (1974)

    Article  Google Scholar 

  13. R. Briere, H. Lemaire, A. Rassat, Bull. Soc. Chim. France 3273 (1965)

  14. G. Grampp, S. Landgraf, I.A. Grigor’ev, A.B. Shapiro, A.I. Kokorin, Appl. Magn. Reson. 19, 187 (2000)

    Article  Google Scholar 

  15. G. Mamantov, A.I. Popov (eds.), Chemistry of Nonaqueous Solutions (VCH, Weinheim, 1994)

  16. R.D. Rogers, K.R. Seddon (eds.), Ionic Liquids: Fundamentals, Progress, Challenges and Opportunities, vols. 901 and 902 of ACS Symposium Series (Oxford University Press, New York, 2005)

  17. J. Phys. Chem. B, 111(18), 4667–4866 (2007). Special issue

    Google Scholar 

  18. Acc. Chem. Res. 40(11), 1077–1236 (2007). Special issue

  19. J.G. Huddleston, A.E. Visser, W.M. Reichert, H.D. Willauer, G.A. Broker, R.D. Rogers, Green Chem. 3, 156 (2001)

    Article  Google Scholar 

  20. S.N. Baker, G.A. Baker, F.V. Bright, Green Chem. 4, 165 (2002)

    Article  Google Scholar 

  21. N. Ito, R. Richert, J. Phys. Chem. B 111, 5016 (2007)

    Article  Google Scholar 

  22. V.A. Tran, K. Rasmussen, G. Grampp, A.I. Kokorin, Mol. Phys. 105, 2119 (2007)

    Article  ADS  Google Scholar 

  23. V.A. Tran, A.I. Kokorin, G. Grampp, K. Rasmussen, Appl. Magn. Reson. 35, 389 (2009)

    Article  Google Scholar 

  24. A. Nakajima, H. Ohya-Nishiguchi, Y. Deguchi, Bull. Chem. Soc. Jpn. 45, 713 (1972)

    Article  Google Scholar 

  25. A.I. Kokorin, V.N. Parmon, V.I. Suskina, Y.A. Ivanov, E.G. Rozantsev, K.I. Zamaraev, Russ. J. Phys. Chem. 48, 548 (1974)

    Google Scholar 

  26. V.N. Parmon, A.I. Kokorin, G.M. Zhidomirov, J. Magn. Reson. 28, 339 (1977)

    Google Scholar 

  27. P. Wasserscheid, T. Waldon (eds.), Ionic Liquid in Synthesis (VCH, Weinheim, 2004)

  28. T. Welton, Chem. Rev. 99, 2071 (1999)

    Article  Google Scholar 

  29. E.G. Rozantsev, G.F. Pavelko, A.L. Buchachenko, M.B. Neiman, Izv. AN SSSR, Ser. Khim. 2306 (1967)

  30. E.G. Rozantsev, V.D. Sholle, Organic Chemistry of Free Radicals (Khimiya, Moscow, 1979)

    Google Scholar 

  31. A.J. McLean, M.J. Muldoon, C.M. Gordon, I.R. Dunkin, Chem. Commun. 1880 (2002)

  32. J.A. Riddick, W.B. Bunger, K.T. Sakano, Techniques of Chemistry. Vol. II: Organic Solvents, Physical Chemistry and Methods of Purification (Wiley, New York, 1986)

    Google Scholar 

  33. Y.N. Molin, K.M. Salikhov, K.I. Zamaraev, Spin Exchange (Springer, Berlin, 1980)

    Google Scholar 

  34. C. Chiappe, D. Pieraccini, J. Org. Chem. 69, 6059 (2004)

    Article  Google Scholar 

  35. K.R. Harris, M. Kanakubo, L.A. Woolf, J. Chem. Eng. Data 51, 1161 (2006)

    Article  Google Scholar 

  36. A. Triolo, O. Russina, H.-J. Bleif, E. Di Cola, J. Phys. Chem. B 111, 4641 (2007)

    Article  Google Scholar 

  37. D. Xiao, J.R. Rajian, A. Cady, S. Li, R.A. Bartsch, E.L. Quitevis, J. Phys. Chem. B 111, 4669 (2007)

    Article  Google Scholar 

  38. V.N. Parmon, A.I. Kokorin, G.M. Zhidomirov, K.I. Zamaraev, Mol. Phys. 26, 1565 (1973)

    Article  ADS  Google Scholar 

  39. V.N. Parmon, A.I. Kokorin, K.I. Zamaraev, Izv. AN SSSR, Ser. Khim. 1776 (1976)

Download references

Acknowledgments

We thank the Russian Foundation for Basic Research (grant 08-03-00478) for financial support of the work.

Author information

Authors and Affiliations

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

    A. I. Kokorin & G. A. Vorobieva

  2. University of Hanoi, Hanoi, Vietnam

    V. A. Tran

Authors
  1. A. I. Kokorin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. A. Tran
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. A. Vorobieva
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. I. Kokorin.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kokorin, A.I., Tran, V.A. & Vorobieva, G.A. Features of Spin Exchange in Short-Chain Nitroxide Biradicals in Ionic Liquids. Appl Magn Reson 37, 473–481 (2010). https://doi.org/10.1007/s00723-009-0073-8

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00723-009-0073-8

Keywords

Search

Navigation