Advertisement

Research on Chemical Intermediates

, Volume 29, Issue 1, pp 1–10 | Cite as

Electron transfer reaction of 4,4′-bipyridine with triethylamine in acetonitrile: effect of water addition on the reaction dynamics

  • Sameh S. Ali
  • K. Maeda
  • H. Murai
  • T. Azumi
Article

Abstract

The photo-induced electron-transfer reaction of 4,4′-bipyridine (BPY) with triethylamine (TEA) in acetonitrile is studied by laser flash photolysis. The reaction mechanism and kinetics are found very sensitive to the presence of a small amount of water. At low water concentrations (i.e. <0.003 M), an extremely fast-rising metastable product is detected for the first time. A triplet charge transfer complex (3ECT) is found to be the primary intermediate preceding the electron transfer process. Up to about 0.1 M, water facilitates the electron transfer rate, whereas higher water concentrations retard the rate of electron transfer. The Stern-Volmer plot of the triplet decay rate versus the TEA concentration is consistent with the presence of 3ECT in equilibrium with the free excited triplet state of BPY.

ELECTRON TRANSFER 4 4'-BIPYRIDINE TRIETHYLAMINE TRIPLET CHARGE TRANSFER COMPLEX 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

REFERENCES

  1. 1.
    S. Nagakura, in: Excited States, E. C. Lim (Ed.), Vol. 2, pp. 322–383. Academic Press, New York, NY (1975).Google Scholar
  2. 2.
    N. G. Turro, Modern Molecular Photochemistry. University Science Books, Mill Valley, CA (1991).Google Scholar
  3. 3.
    A. Weller, Z. Phys. Chem. 17, 224 (1958).Google Scholar
  4. 4.
    M. Mataga and Y. Kaifu, J. Chem. Phys. 36, 2804 (1962).Google Scholar
  5. 5.
    M. Mataga and Y. Kaifu, Mol. Phys. 7, 137 (1963).Google Scholar
  6. 6.
    H. Beens, K. H. Grellmann, M. Gurr and A. Weller, Discuss. Faraday Soc. 39, 183 (1965).Google Scholar
  7. 7.
    W. R. Ware, P. R. Shukla, P. J. Sullivan and R. V. Bremphis, J. Chem. Phys. 55, 4048 (1971).Google Scholar
  8. 8.
    M. Ofran and J. Feitelson, Chem. Phys. Lett. 19, 427 (1973).Google Scholar
  9. 9.
    A. Matsuzaki, K. Yoshihara and S. Nagakura, Bull. Chem. Soc. Jpn. 47, 1152 (1974).Google Scholar
  10. 10.
    T. Kiyota, M. Yamaji and H. Shizuka, J. Phys. Chem. 100, 672 (1996).Google Scholar
  11. 11.
    G. Buntinx, A. Benbouazza, O. Poizat and V. Guichard, Chem. Phys. Lett. 153, 279 (1988).Google Scholar
  12. 12.
    O. Poizat, G. Buntinx, M. Ventura and M. F. Lautié, J. Phys. Chem. 95, 1225 (1991).Google Scholar
  13. 13.
    O. Poizat, G. Buntinx, P. Valat, V. Wintgens and M. Bridoux, J. Phys. Chem. 97, 5905 (1993).Google Scholar
  14. 14.
    O. Poizat and G. Buntinx, J. Phys. Chem. 99, 9403 (1995).Google Scholar
  15. 15.
    G. Buntinx, P. Valat, V. Wintgens and O. Poizat, J. Phys. Chem. 95, 9347 (1991).Google Scholar
  16. 16.
    F. Elesei, U. Mazzucato, H. Görner and D. Schulte-Frohlinde, J. Photochem. Photobiol. 50A, 209 (1989).Google Scholar
  17. 17.
    M. Simic and M. Ebert, Int. J. Radiat. Phys. Chem. 3, 259 (1971).Google Scholar
  18. 18.
    J. Lu, J. M. Cotton, R. L. Birke and J. R. Lombardi, Langmuir 5, 406 (1989).Google Scholar
  19. 19.
    M. Yamaji, T. Sekiguchi, M. Hoshino and H. Shizuka, J. Phys. Chem. 96, 9353 (1992).Google Scholar
  20. 20.
    S. S. Ali, K. Maeda, H. Murai and T. Azumi, Chem. Phys. Lett. 267, 520 (1997).Google Scholar
  21. 21.
    S. Kohno, M. Hoshino and H. Shizuka, J. Phys. Chem. 95, 5489 (1991).Google Scholar
  22. 22.
    S. M. Hubig and J. K. Kochi, J. Am. Chem. Soc. 121, 1688 (1999).Google Scholar
  23. 23.
    R. Rathore, S. M. Hubig and J. K. Kochi, J. Am. Chem. Soc. 119, 11468 (1997).Google Scholar
  24. 24.
    P. Piotrowiak, Chem. Soc. Rev. 28, 143 (1999).Google Scholar
  25. 25.
    J. Mayer, D. Hrovat, J. Thomas and W. Borden, J. Am. Chem. Soc. 124, 11142 (2002).Google Scholar
  26. 26.
    N. Bunce, S. Cater, J. Scaiano and L. Johnston, J. Org. Chem. 52, 4214 (1987).Google Scholar
  27. 27.
    H. Görner, D. Döpp and A. Dittmann, J. Chem. Soc., Perkin Trans. 2, 1723 (2000).Google Scholar
  28. 28.
    H. Görner and D. Döpp, J. Chem. Soc., Perkin Trans. 2, 120 (2002).Google Scholar

Copyright information

© VSP 2003 2003

Authors and Affiliations

  • Sameh S. Ali
  • K. Maeda
  • H. Murai
  • T. Azumi

There are no affiliations available

Personalised recommendations