Advertisement

Russian Chemical Bulletin

, Volume 47, Issue 8, pp 1466–1471 | Cite as

The influence of excitation of the 4f-orbital of Eu(fod)3 on complex formation with adamantanone and anomalous enhancement of Eu3+ luminescence under the action of H2O and D2O molecules in toluene

  • S. S. Ostakhov
  • A. I. Voloshin
  • V. P. Kazakov
  • N. M. Shavaleev
Physical Chemistry

Abstract

The influence of excitation of the 4f-orbital of, β-diketonate Eu(fod)3 (fod is heptafluorodimethyloctanedione) on the formation of the coordination bond with adamantanone (1) was studied by the nonradiative energy transfer technique. The kinetic parameters of fluorescence (FL) and the lifetime (τ) of the Eu3+ ion in toluene solutions were studied. The increase in the stability of the Eu(fod)3·1 complex when f—f-transitions of the Eu3+ ion are excited is related to an increase in the acceptor capability of Eu(fod)3 due to the increasing fraction of the covalent component determined by the participation of 4f-orbitals. An unexpected effect of enhancement of the Eu(fod)3 fluorescence under the action of H2O (D2O) molecules in toluene solutions was observed. The effect is assumed to be caused by an increase in the negative inductive effect when outer-sphere associates with the fluorinated radical of β-diketonate are formed. The mechanisms of the influence of electron-donating inner-sphere ligands and outer-sphere associates on the quantum yield of fluorescence of Eu(fod)3 are discussed.

Key words

fluorescence, nonradiative energy transfer Eu(iii) β-diketonate, adamantanone, complex formation 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    V. L. Ermolaev, E. I. Bodunov, E.B. Sveshnikova, and T. A. Shakhverdov,Bezyzluchatel'nyi perenos energii vozbuzhdeniya [Nonradiative Transfer of Excitation Energy], Nauka, Leningrad, 1977, 311 pp. (in Russian).Google Scholar
  2. 2.
    M. I. Gaiduk, V. F. Zolin, and L. S. Gaigerova,Spektry lyuminestsentsii evropiya [Luminescence Spectra of Europium], Nauka, Moscow, 1974, 195 pp. (in Russian).Google Scholar
  3. 3.
    V. L. Ermolaev and E. B. Sveshnikova,Usp. Khim., 1994,63, 962 [Russ. Chem. Rev., 1994,63 (Engl. Transl.)].Google Scholar
  4. 4.
    V. L. Ermolaev, E. B. Sveshnikova, and E. N. Bodunov,Usp. Fiz. Nauk, 1996,166, 279 [Russ. Phys. Rev., 1996,166 (Engl. Transl.)].CrossRefGoogle Scholar
  5. 5.
    V. E. Karasev, A. G. Mirochnik, and E. N. Murav'ev,Zh. Neorg. Khim., 1984,29, 259 [J. Inorg. Chem. USSR, 1984,29 (Engl. Transl.)].Google Scholar
  6. 6.
    E. F. Kustov, G. A. Bandurkin, E. N. Murav'ev, and V. P. Orlovskii,Elektronnye spektry soedinenii redkozemel'nykh elementov [Electronci Spectra of Compounds of Rare-Earth Elements], Nauka, Moscow, 1981, 303 pp (in Russian).Google Scholar
  7. 7.
    G. L. Sharipov, V. P. Kazakov, and G. A. Tolstikov,Khimiya i khemilyuminestsentsiya 1,2-dioksetanov [Chemistry and Chemiluminescence of 1,2-Dioxetanes], Nauka, Moscow, 1990, 288 pp. (in Russian).Google Scholar
  8. 8.
    G. B. Schuster, N. J. Turro, H.-C. Steinmetzer, A. P. Schaap, G. Faler, W. Adam, and J. C. Liu,J. Am. Chem. Soc., 1975,97, 7110.CrossRefGoogle Scholar
  9. 9.
    R. A. Gundmundsen, O. J. Marsh, and E. Matovich,J. Chem. Phys., 1963,39, 272.CrossRefGoogle Scholar
  10. 10.
    K. B. Yatsimirskii, N. A. Kostromina, Z. A. Sheka, N. K. Davidenko, E. E. Kriss, and V. I. Ermolenko,Khimiya kompleksnykh soedinenii redkozemel'nykh elementov [Chemistry of Complex Compounds of Rare-Earth Elements], Naukova Dumka, Kiev, 1966, 493 pp. (in Russian).Google Scholar
  11. 11.
    G. Stein and E. Wurzberg,J. Chem. Phys., 1975,62, 208.CrossRefGoogle Scholar
  12. 12.
    G. L. Kropp and M. W. Windsor,J. Phys. Chem., 1967,71, 477.CrossRefGoogle Scholar
  13. 13.
    E. B. Sveshnikova, V. F. Morina, and V. L. Ermolaev,Optika i spektroskopiya [Optics and Spectroscopy], 1974,36, 725 (in Russian).Google Scholar
  14. 14.
    S. S. Ostakhov, A. I. Voloshin, V. P. Kazakov, and I. A. Khusainova,Khim. Fiz., 1997,16, 84 [Chem. Phys. Reports, 1997,16 (Engl. Transl.)].Google Scholar
  15. 15.
    S. S. Ostakhov, A. I. Voloshin, V. P. Kazakov, and I. A. Khusainova,Khim. Fiz., 1997,16, 79 [Chem. Phys. Reports, 1997,16 (Engl. Transl.)].Google Scholar
  16. 16.
    M. D. Marcantonatos, M. Deschaux, and J. J. Vuilleumier,Chem. Phys. Lett., 1981,82, 36.CrossRefGoogle Scholar
  17. 17.
    S. S. Ostakhov, V. P. Kazakov, D. D. Afonichev, and V. V. Rykova,Radiokhimiya, 1995,37, 503 [Radiochemistry, 1995,37 (Engl. Transl.)].Google Scholar
  18. 18.
    N. Sh. Ableeva, A. I. Voloshin, S. S. Ostakhov, V. P. Kazakov, and G. L. Tolstikov,Khim. Fiz., 1996,15, 34 [Chem. Phys. Reports, 1996,15, 345 (Engl. Transl.)].Google Scholar
  19. 19.
    V. P. Gruzdev,Zh. Neorg. Khim., 1977,22, 3208 [J. Inorg. Chem. USSR, 1977,22 (Engl. Transl.)].Google Scholar
  20. 20.
    D. J. Raber, M. D. Johnston, C. M. Janks, J. W. Perry, and G. F. Jackson,Organ. Magnet. Resonance, 1980,14, 32.CrossRefGoogle Scholar
  21. 21.
    A. I. Voloshin, G. L. Sharipov, V. P. Kazakov, and G. A. Tolstikov,Izv. Akad. Nauk, Ser. Khim., 1992, 1056 [Bull. Russ. Acad. Sci., Div. Chem. Sci., 1992,41, 828 (Engl. Transl.)].Google Scholar
  22. 22.
    N. Sh. Ableeva, A. I. Voloshin, E. V. Vasil'eva, G. L. Sharipov, L. M. Khalilov, V. P. Kazakov, and G. A. Tolstikov,Kinet. Katal., 1993,34, 881 [Kinet. Catal., 1993,34 (Engl. Transl.)].Google Scholar
  23. 23.
    Y. Haas and G. Stein,J. Phys. Chem., 1971,75, 3677.CrossRefGoogle Scholar
  24. 24.
    V. S. Tachin, V. L. Ermolaev, and E. N. Bodunov,Zh. Neorg. Khim., 1975,20, 341 [J. Inorg. Chem. USSR, 197520 (Engl. Transl.)].Google Scholar
  25. 25.
    D. J. Karraker,J. Inorg. Nucl. Chem., 1971,33, 3713.CrossRefGoogle Scholar
  26. 26.
    J. L. Kropp and M. W. Windsor,J. Chem. Phys., 1965,42, 1599.CrossRefGoogle Scholar

Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • S. S. Ostakhov
    • 1
  • A. I. Voloshin
    • 1
  • V. P. Kazakov
    • 1
  • N. M. Shavaleev
    • 1
  1. 1.Institute of Organic ChemistryUfa Research Center of the Russian Academy of SciencesUfaRussian Federation

Personalised recommendations