Skip to main content
SpringerLink
Log in

ESR and ENDOR investigations of the degenerate electron exchange reactions of various viologens in solution. Solvent dynamical effects

  • Published:
Applied Magnetic Resonance Aims and scope Submit manuscript

Abstract

The temperature dependences of the rates of the degenerate electron transfer of various viologens (1,1′-di(hydrocarbyl)-4,4′-bipyridinium salts) are measured in seven different solvents by means of electron spin resonance (ESR) line broadening. Rates vary between 1.7·108 and 1.1·109 M−1s−1 at room temperature and clearly show a solvent dynamical effect, which is inferred from the dependence of the rate constants on the longitudinal relaxation time of the solvent. Activation energies ranging from 5.3 to 24.4 kJ mol−1 are found. For the first time, hyperfine coupling constants are reported for the radical cations of the hydroxyethyl viologen and the amino viologen based on both continuous-wave ESR and electron-nuclear double resonance spectroscopy. Furthermore, the temperature and the solvent dependence of the hyperfine coupling constants of the methyl viologen radical cation 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

Similar content being viewed by others

References

  1. Monk P.M.S.: The Viologens. Chichester: Wiley 1998.

    Google Scholar 

  2. Summers L.A.: The Bipyridinum Herbicides. London: Academic Press 1980.

    Google Scholar 

  3. Summers L.A.: Adv. Heterocycl. Chem.35, 281–374 (1984)

    Article  Google Scholar 

  4. Bird C.L., Kuhn A.T.: Chem. Soc. Rev.10, 49–82 (1981)

    Article  Google Scholar 

  5. Sliwa W., Bachowska B., Zelichowicz N.: Heterocycles32, 2241–2273 (1991)

    Article  Google Scholar 

  6. Johnson Jr. C.S., Gutowsky H.S.: J. Chem. Phys.39, 58–62 (1963)

    Article  ADS  Google Scholar 

  7. Kuczynski J.P., Molsavljevic B.H., Lappin A.G., Thomas J.K.: Chem. Phys. Lett.104, 149–152 (1984)

    Article  ADS  Google Scholar 

  8. Evans A.G., Evans J.C., Baker M.W.: J. Chem. Soc. Perkin Trans. II1977, 1787–1789.

  9. Evans J.C., Evans A.G., Nouvi-Sorkhabi N.H., Obaid A.Y., Rowlands C.C.: J. Chem. Soc. Perkin Trans. II1985, 315–318.

  10. Evans J.C., Nouvi-Sorkhabi M.H., Rowlands C.C.: Tetrahedron38, 2581–2584 (1982)

    Article  Google Scholar 

  11. Lee C.W., Eklund J.C., Dryfe R.A.W., Compton R.G.: Bull. Korean Chem. Soc.17, 162–167 (1996)

    Google Scholar 

  12. Evans A.G., Evans J.C., Baker M.W.: J. Chem. Soc. Perkin Trans. II1977, 1972–1999.

  13. Dunham W.R., Fee J.A., Harding L.J., Grande H.J.: J. Magn. Reson.40, 351–359 (1980)

    Google Scholar 

  14. Deuchert K., Hünig S.: Angew. Chem.90, 927–938 (1978)

    Article  Google Scholar 

  15. Fuhlendorff R., Lund T., Pedersen J.A.: Tetrahedron Lett.28, 5335–5338 (1987)

    Article  Google Scholar 

  16. Rieger A.L., Rieger P.H.: J. Phys. Chem.88, 5845–5851 (1984)

    Article  Google Scholar 

  17. Curtis J.C., Sullivan B.P., Meyer T.J.: Inorg. Chem.19, 3833–3839 (1980)

    Article  Google Scholar 

  18. Andrade de Oliveira L.A., Haim A.: J. Am. Chem. Soc.104, 3363–3366 (1982)

    Article  Google Scholar 

  19. Gu N., Dong S.: Electrochem. Commun.2, 713 (2000)

    Article  Google Scholar 

  20. Marcus R.A., Sutin N.: Biochim Biophys. Acta811, 265–322 (1985)

    Google Scholar 

  21. Riddick J.A., Bunger W.B., Sakano K.T.: Techniques of Chemistry, Organic Solvents, Physical Properties and Methods of Purification, vol. II. New York: Wiley 1986.

    Google Scholar 

  22. Buchner R., Barthel J., Stauber J.: Chem. Phys. Lett.306, 57 (1999)

    Article  ADS  Google Scholar 

  23. Sato T., Buchner R.: J. Phys. Chem. A108, 5007 (2004)

    Article  Google Scholar 

  24. Shrike R.M., Chaudhari A., More N.M., Patil P.B.: J. Mol. Liq.94, 27 (2001)

    Article  Google Scholar 

  25. Barthel J., Bachuber K., Buchner R., Gill J.B., Kleebauer M.: Chem. Phys. Lett.167, 62 (1990)

    Article  ADS  Google Scholar 

  26. Barthel J., Buchner R., Hötzl C.G., Münsterer M.: Z. Phys. Chem.214, 1213 (2000)

    Google Scholar 

  27. Barthel J., Buchner R., Wurm B.: J. Mol. Liq.98, 51 (2002)

    Article  Google Scholar 

  28. Chaudhari A., Chaudhari H., Mehrotra S.: Fluid Phase Equilib.201, 107 (2002)

    Article  Google Scholar 

  29. Khirade P.W., Chaudhari A., Shinde J.B., Helambe S.N., Mehrotra S.C.: J. Chem. Eng. Data44, 879 (1999)

    Article  Google Scholar 

  30. Tsukahara K., Wilkins R.G.: J. Am. Chem. Soc.107, 2632–2635 (1985)

    Article  Google Scholar 

  31. Grampp G.: Spectrochim. Acta A54, 2349–2358 (1998)

    Article  Google Scholar 

  32. Freed J.H.: J. Phys. Chem.71, 38–51 (1967)

    Article  Google Scholar 

  33. Hyde J.S.: Appl. Magn. Reson.1, 483–496 (1990)

    Article  Google Scholar 

  34. Sano H., Tachya M.: J. Chem. Phys.71, 1276–1282 (1979)

    Article  ADS  Google Scholar 

  35. Sutin N.: Adv. Chem. Phys.106, 7–33 (1999)

    Article  Google Scholar 

  36. Bixon M., Jortner J.: Adv. Chem. Phys.106, 35–201 (1999)

    Article  Google Scholar 

  37. Marcus R.A.: J. Chem. Phys.24, 966–989 (1956)

    Article  ADS  Google Scholar 

  38. Hostein T.: Philos. Mag. B37, 499–526 (1978)

    Article  Google Scholar 

  39. Nelsen S.F., Blackstock S.C., Kim Y.: J. Am. Chem. Soc.109, 677–682 (1987)

    Article  Google Scholar 

  40. Kelterer A., Landgraf S., Grampp G.: Spectrochim. Acta A57, 1959–1969 (2001)

    Article  Google Scholar 

  41. Noyes R.M.: Prog. React. Kinet.1, 129–160 (1961)

    Google Scholar 

  42. Marcus R.A.: Disc. Faraday Soc.29, 21–31 (1960)

    Article  Google Scholar 

  43. Debye P.: Trans. Am. Electrochem. Soc.82, 265–272 (1942)

    Google Scholar 

  44. German E.D., Kuznetsov A.M.: Electrochim. Acta26, 1595–1608 (1981)

    Article  Google Scholar 

  45. Kharkats Yu.I.: Elektrokhimiya12, 1284–1291 (1976)

    Google Scholar 

  46. Ross J.H., Krieger R.I.: J. Agric. Food Chem.28, 1026–1031 (1980)

    Article  Google Scholar 

  47. Gnerin-Outer D., Niccollin C.: Mol. Phys.34, 161 (1977)

    Article  ADS  Google Scholar 

  48. Sullivan P.D., Menger E.M.: Adv. Magn. Reson.9, 1–48 (1977)

    Google Scholar 

  49. Grampp G., Jaenicke W.: Ber. Bunsenges. Phys. Chem.95, 904–927 (1991)

    Google Scholar 

  50. Zusman L.D.: Chem. Phys.49, 295–304 (1980);80, 29–43 (1983);119, 51–61 (1988);144, 1–6 (1990)

    Article  MathSciNet  ADS  Google Scholar 

  51. Zusman L.D.: Z. Phys. Chem.186, 1–29 (1994)

    Article  Google Scholar 

  52. Rips I., Jortner J.: J. Chem. Phys.87, 2090–2104 (1987)

    Article  ADS  Google Scholar 

  53. Marcus R.A., Sumi H.: J. Chem. Phys.84, 4894–4914 (1986)

    Article  ADS  Google Scholar 

  54. Nadler W., Marcus R.A.: J. Chem. Phys.86, 3908–3924 (1987)

    ADS  Google Scholar 

  55. Hynes J.T.: J. Phys. Chem.90, 3701–3706 (1986)

    Article  Google Scholar 

  56. Heitele H.: Angew. Chem. Int. Ed. Engl.32, 359–377 (1993)

    Article  Google Scholar 

  57. Bagchi B., Gayathri N.: Adv. Chem. Phys.107, 1–80 (2002)

    Article  Google Scholar 

  58. Barzykin A.V., Frantsuzov P.A., Seki K., Tachiya M.: Adv. Chem. Phys.123, 511–616 (2002)

    Article  Google Scholar 

  59. Sumi H.: Adv. Chem. Phys.107, 601–646 (1999)

    Article  Google Scholar 

  60. Friedman H.L.: J. Chem. Soc. Faraday Trans.79, 1465–1467 (1983)

    Article  Google Scholar 

  61. Kivelson D., Friedman H.L.: J. Phys. Chem.93, 7026–7031 (1989)

    Article  Google Scholar 

  62. Beratan D.N., Onuchic J.N.: J. Chem. Phys.89, 6195–6203 (1988)

    Article  ADS  Google Scholar 

  63. Onuchic J.N., Beratan D.N.: J. Phys. Chem.92, 4817–4820 (1988)

    Article  ADS  Google Scholar 

  64. Fawcett W.R., Foss C.: J. Electroanal. Chem.270, 103–118 (1989)

    Article  Google Scholar 

  65. Weaver M.J.: Chem. Rev.92, 463–480 (1992)

    Article  Google Scholar 

  66. Barthel J., Bachhuber K., Buchner R., Gill J.B., Kleebauer M.: Chem. Phys. Lett.167, 62–66 (1990)

    Article  ADS  Google Scholar 

  67. Fukuzumi S., Endo Y.: J. Am. Chem. Soc.124, 10974–10975 (2002)

    Article  Google Scholar 

  68. Vener M., Ioffe N.T., Cheprakov A.V., Mairanovsky V.G.: J. Electroanal. Chem.370, 33–39 (1994)

    Article  Google Scholar 

  69. Grampp G., Landgraf S., Rasmussen K.: J. Chem. Soc. Perkin Trans. II1999, 1897–1899.

  70. Lü J.M., Wen X.L., Wu L.M., Lin Y.C., Liu Y.C.: J. Phys. Chem. A105, 6971–6975 (2001)

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Graz University of Technology, Technikerstraße 4/I, 8010, Graz, Austria

    G. Grampp, B. Y. Mladenova, D. R. Kattnig & S. Landgraf

Authors
  1. G. Grampp
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. B. Y. Mladenova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. D. R. Kattnig
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. Landgraf
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Grampp, G., Mladenova, B.Y., Kattnig, D.R. et al. ESR and ENDOR investigations of the degenerate electron exchange reactions of various viologens in solution. Solvent dynamical effects. Appl. Magn. Reson. 30, 145–164 (2006). https://doi.org/10.1007/BF03166715

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF03166715

Keywords

Search

Navigation