Intermediates in Photochemistry of Fe(III) Complexes in Water

  • Victor Plyusnin
  • Ivan Pozdnyakov
  • Eugeny Glebov
  • Vjacheslav Grivin
  • Nikolai Bazhin
Conference paper
Part of the NATO Science for Peace and Security Series C: Environmental Security book series (NAPSC)


The photochemistry of Fe(OH)2+ complex and complexes formed by Fe(III) and pyruvic (Pyr), tartaric (Tart), sulfosalycilic (SSA) and oxalic (Ox) acids in aqueous solutions were studied by means of stationary and nanosecond laser flash photolysis. The application of different scavengers of transient radicals has shown that the hydroxyl radical is the primary photochemical species in photochemistry of the FeOH2+ complex. In the photochemistry of FePyr2+ and FeTart+ complexes a weak absorption was found in the red spectral region which was attributed to [FeII…R-COO]2+ radical complexes. Laser flash photolysis of FePyr2+ and FeTart+ complexes in the presence of methyl viologen (effective scavenger of different free radicals) gave evidence of MV•2+ radical cation formation with concentration as small as ~2% of Fe(III) complex disappeared. The reaction mechanism including inner-sphere electron transfer with the formation of [FeII…R-COO]2+ radical complex and its transformation to the reaction products is proposed. The main photochemical process for FeIII(C2O4)33— complex in aqueous solutions was found to be intramolecular electron transfer from the ligand to Fe(III) ion with the formation of a primary radical complex [(C2O4)2FeII(C2O4•)]3−. The yield of free radical species (i.e., CO2•− and C2O4•−) was found to be less then 6% of FeIII(C2O4)33— disappeared after a laser pulse.


photochemical process Fe (III) complexes organic acid ligands laser flash photolysis 


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  1. 1.
  2. 2.
    Benkenberg H-J, Warneck P (1995) J Phys Chem, 99: 5214.CrossRefGoogle Scholar
  3. 3.
    Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) J Phys Chem Ref Data, 17: 513.Google Scholar
  4. 4.
    Nansheng D, Feng W, Fan L, Mei X (1998) Chemosphere, 36: 3101.CrossRefGoogle Scholar
  5. 5.
    Watanabe T, Honda K (1982) J Phys Chem, 86: 179.Google Scholar
  6. 6.
    Grivin VP, Khmelinski IV, Plyusnin VF, Blinov II, Balashev KP (1990) J Photochem Photobiol A:Chem, 51: 167.CrossRefGoogle Scholar
  7. 7.
    Ivanov KL, Glebov EM, Plyusnin VF, Ivanov YuV, Grivin VP, Bazhin NM (1999) React Kinet Catal Lett, 66: 163.CrossRefGoogle Scholar
  8. 8.
    Pozdnyakov IP, Glebov EM, Plyusnin VF, Grivin VP, Ivanov YuV, Vorobyev DYu, Bazhin NM (2000) Pure Appl Chem, 72: 2187.CrossRefGoogle Scholar
  9. 9.
    Pozdnyakov IV, Glebov EM, Plyusnin VF, Grivin VP, Ivanov YuV, Bazhin NM, Vorobjev DYu (2000) Mendeleev Commun, 10: 185.CrossRefGoogle Scholar
  10. 10.
    Pozdnyakov IP, Sosedova YuA, Plyusnin VF, Glebov EM, Grivin VP, Vorobyev DYu, Bazhin NM (2004) Int J Photoenergy, 6: 89.CrossRefGoogle Scholar
  11. 11.
    Pozdnyakov IP, Sosedova YuA, Plyusnin VF, Grivin VP, Vorobyev DYu, Bazhin NM (2004) Russian Chem Bull, International Edition, 53: 2715.CrossRefGoogle Scholar
  12. 12.
    Asmus K-D, Cercek B, Evert M, Henglein A (1967) Wigger A Trans Faraday Soc, 63: 2435.CrossRefGoogle Scholar
  13. 13.
    Hayon E, Ibata T, Lichtin NN, Simic M (1970) J Am Chem Soc, 92: 3898.CrossRefGoogle Scholar
  14. 14.
    Land EJ, Ebert M (1967) Trans Far Soc, 63: 1181.CrossRefGoogle Scholar
  15. 15.
    Field RJ, Raghavan NV, Drummer JG (1982) J Phys Chem, 86: 2443.CrossRefGoogle Scholar
  16. 16.
    Swift TJ, Connick RE (1962) J Chem Phys, 37: 307.CrossRefGoogle Scholar
  17. 17.
    Wang L, Zhang Ch, Wu F, Deng N, Glebov EM, Bazhin NM (2006) React Kinet Catal Lett, 89: 183.CrossRefGoogle Scholar
  18. 18.
    Ghandour M, Mansour H, Abu E, Moustafa H, Khodary M (1988) J Indian Chem Soc, 65: 827.Google Scholar
  19. 19.
    Das A, Mukhopadhayay S (2004) Trans Metal Chem, 29: 797.CrossRefGoogle Scholar
  20. 20.
    Luyr'e YuYu (1967) Spravochnik Po Analiticheskoi Khimii (Analytical Chemistry Handbook). Khimiya, Moscow: 248 p. (in Russian).Google Scholar
  21. 21.
    Feng W, Deng N, Glebov EM, Pozdnyakov IP, Grivin VP, Plyusnin VF, Bazhin NM (2007) Russian Chem Bull, International Edition, 56: 900.CrossRefGoogle Scholar
  22. 22.
    Lur'e YuYu (1979) Spravochnik po analiticheskoi khimii (Handbook on Analytic Chemistry). Khimiya, Moscow: 344 p. (in Russian).Google Scholar
  23. 23.
    Wang J, Tateno T, Sakuragi H, Tokumaru K (1995) J Photochem Photobiol A: Chem, 92: 53.CrossRefGoogle Scholar
  24. 24.
    Pozdnyakov IP, Plyusnin VF, Grivin VP, Vorobyev DYu, Bazhin NM, Pagӥs S, Vauthey E (2006) J Photochem Photobiolog A: Chem, 182: 75.CrossRefGoogle Scholar
  25. 25.
    Pozdnyakov IP, Plyusnin VF, Tkachenko N, Lemmetyinen H (2007) Chem Phys Lett, 445: 203.CrossRefGoogle Scholar
  26. 26.
    Ogawa K, Tobe N (1966) Bull Chem Soc Japan, 39: 223–227.CrossRefGoogle Scholar
  27. 27.
    Son DH, Kambhampati P, Kee TW, Barbara PF (2002) J Phys Chem A, 106, 4591.CrossRefGoogle Scholar
  28. 28.
    Pozdnyakov IP, Kel OV, Plyusnin VF, Grivin VP, Bazhin NM (2008) J Phys Chem A, 112: 8316.CrossRefGoogle Scholar
  29. 29.
    Zuo Y, Zhan J (2005) Atm Environ, 39: 27.CrossRefGoogle Scholar
  30. 30.
    Calvert J, Pitts J (1967) Photochemistry. Wiley, New York-London-Sydney.Google Scholar
  31. 31.
    Balzani V, Carassiti V (1970) Photochemistry of Coordination Compounds. Academic Press, London-New York.Google Scholar
  32. 32.
    Parker CA, Hatchard CG (1955) Nature, 176: 122.CrossRefGoogle Scholar
  33. 33.
    Nadtochenko V, Kiwi J (1996) J Photochem Photoboil A: Chem, 99: 145.CrossRefGoogle Scholar
  34. 34.
    Patterson JIH, Perone SP (1973) J Phys Chem, 77: 2437.CrossRefGoogle Scholar
  35. 35.
    Cooper GD, DeGraff BA (1971) J Phys Chem, 75: 2897.CrossRefGoogle Scholar
  36. 36.
    Chen J, Zhang H, Tomov IV, Wolfsberg M, Ding X, Rentzepis PM (2007) J Phys Chem A, 111: 9326.CrossRefGoogle Scholar

Copyright information

© Springer Science + Business Media B.V. 2009

Authors and Affiliations

  • Victor Plyusnin
    • 1
  • Ivan Pozdnyakov
    • 1
  • Eugeny Glebov
    • 1
  • Vjacheslav Grivin
    • 1
  • Nikolai Bazhin
    • 1
  1. 1.Institute of Chemical Kinetics and Combustion SB RAS, Institutskaya 3NovosibirskRussia

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