Intramolecular spin exchange in flexible short-chain biradicals in solutions with various viscosity

  • G. Grampp
  • K. Rasmussen
  • A. I. Kokorin
Article

Abstract

Intramolecular electron spin exchange as a function of temperature and solvent viscosity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two short-chain flexible nitroxide biradicals. Certain thermodynamic parameters of the conformational rearrangements were calculated from the EPR spectra. The process of spin exchange in these biradicals dissolved in six different alcohols is compared with that in a nonpolar solvent (toluene) and with the thermodynamic characteristics of the solvents. No correlation is found on a macroscopic level (solvent viscosity) but on a microscopic level (solvent longitudinal relaxation times) a distinct correlation is seen. The original results are compared with literature data.

Keywords

Electron Paramagnetic Resonance Electron Paramagnetic Resonance Spectrum Nitroxide Cyclohexanol Hexanol 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

References

  1. 1.
    Parmon V.N., Kokorin A.I., Zhidomirov G.M.: J. Struct. Chem.18, 104 (1977); Parmon V.N., Kokorin A.I., Zhidomirov G.M.: Stable Biradicals. Moscow: Nauka 1980.CrossRefGoogle Scholar
  2. 2.
    Rassat A.: Pure. Appl. Chem.25, 623 (1971)CrossRefGoogle Scholar
  3. 3.
    Shapiro A.B., Baimagambetov K., Goldfield M.G., Rozantsev E.G.: Zh. Org. Khim.8, 2263 (1972)Google Scholar
  4. 4.
    Parmon V.N., Kokorin A.I., Zhidomirov G.M., Zamaraev K.I.: Mol. Phys.30, 695 (1975)CrossRefADSGoogle Scholar
  5. 5.
    Molin Yu.N., Salikhov K.M., Zamaraev K.I.: Spin Exchange. Berlin: Springer 1980.Google Scholar
  6. 6.
    Grampp G., Landgraf S., Grigor’ev I.A., Shapiro A.B., Kokorin A.I.: Appl. Magn. Reson.19, 187 (2000)CrossRefGoogle Scholar
  7. 7.
    Alster E., Silver B.L.: Mol. Phys.58, 977 (1986)CrossRefADSGoogle Scholar
  8. 8.
    Shastnev P.V., Salikhov K.M.: Teor. Eksp. Khim.9, 291 (1973)Google Scholar
  9. 9.
    Nedlin G.M.: Fiz. Tverd. Tela (Leningrad)15, 3048 (1973)Google Scholar
  10. 10.
    Rozantsev E.G.: Free Nitroxyl Radicals. New York: Plenum 1970.Google Scholar
  11. 11.
    Shapiro A.B., Suskina V.I.: Izv. Akad. Nauk SSSR Ser. Khim.1986, 1900.Google Scholar
  12. 12.
    Shapiro A.B., Goldfield M.G., Rozantsev E.G.: Tetrahedron Lett.24, 2183 (1973)CrossRefGoogle Scholar
  13. 13.
    Riddick J.A., Bunger W.B., Sakano K.T. in: Techniques of Chemistry, vol. II: Organic Solvents. Physical Properties and Methods of Purification. New York: Wiley 1986.Google Scholar
  14. 14.
    Lemaire H.: J. Chem. Phys.64, 559 (1967)Google Scholar
  15. 15.
    Gulin V.I., Dikanov S.A., Martin V.V., Grigor’ev I.A., Volodarsky L.B.: Izv. Sib. Otd. Akad. Nauk SSSR Ser. Khim. (2)1988, 99.Google Scholar
  16. 16.
    Dikanov S.A., Shchukin G.I., Grigor’ev I.A., Rukin S.I., Volodarsky L.B.: Izv. Akad. Nauk SSSR Ser. Khim.1985, 565.Google Scholar
  17. 17.
    Gilmont R.: Measurement Control2002, 36.Google Scholar
  18. 18.
    Karapet’yants M.Kh., Yen K.-S.: Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol.4, 580 (1961)Google Scholar
  19. 19.
    Glarum S.H., Marshall J.H.: J. Chem. Phys.47, 1374 (1967)CrossRefADSGoogle Scholar
  20. 20.
    Luckhurst G.R.: Mol. Phys.10, 543 (1966)CrossRefADSGoogle Scholar
  21. 21.
    Parmon V.N., Kokorin A.I., Zamaraev K.I.: Izv. Akad. Nauk SSSR Ser. Khim.1976, 1776.Google Scholar
  22. 22.
    Friedman H.L.: J. Chem. Soc. Faraday Trans.79, 1465 (1983); Kivelson D., Friedman H.L.: J. Phys. Chem.93, 7026 (1989).CrossRefGoogle Scholar
  23. 23.
    Grampp G., Rasmussen K.: Phys Chem Chem Phys4, 5546 (2002)CrossRefGoogle Scholar
  24. 24.
    Onganer Y., Yin M., Bessire D.R., Quitevis E.L.: J. Phys. Chem.97, 2344 (1993)CrossRefGoogle Scholar
  25. 25.
    Hanna F.F., Gestblom B., Soliman A.: J. Mol. Liq.95, 27 (2002)CrossRefGoogle Scholar
  26. 26.
    Lou J., Hatton T.A., Laibnis P.E.: J. Phys. Chem. A101, 5262 (1997)CrossRefGoogle Scholar

Copyright information

© Springer 2004

Authors and Affiliations

  • G. Grampp
    • 1
  • K. Rasmussen
    • 1
  • A. I. Kokorin
    • 2
  1. 1.Institute of Physical and Theoretical ChemistryGraz University of TechnologyGrazAustria
  2. 2.N. Semenov Institute of Chemical PhysicsRussian Academy of ScienceMoscowRussian Federation

Personalised recommendations