Proton Transfer

  • Michiya Itoh


Excited-state proton transfer (ESPT) plays a vital role in many systems that are very important to any description of molecular interactions, not only in the field of photochemistry but also in photobiological phenomena. Inter- and intramolecular ESPT, as well as energy and electron transfer, also provide us with fundamental concepts in the design of the photochromic systems found in functional polymers and other molecular assemblies. In 1952, Förster [1] initiated research in the field of intermolecular ESPT with his study of 2-naphthol. He demonstrated that pK a* is the hydroxyl group of 2-naphthol decreased significantly in the singlet excited state compared with the ground state. Further, Weller [2] found that methyl salicylate (MS) presented an unusually large Stokes shifted fluorescence due to intramolecular ESPT. Since their pioneering work on ESPT, numerous investigations have been carried out in both the liquid and the solid state.


Proton Transfer Transient Absorption Potential Energy Curve Methyl Salicylate Double Proton Transfer 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Förster T (1951) Fluoreszenz organischer verbindungen. Vandenboeck & Ruprecht, GöttigenGoogle Scholar
  2. 2.
    Weller A (1955) Fluorescence of salicylic acid and related compounds. Naturwissenschaften 42:175–176CrossRefGoogle Scholar
  3. 3.
    Kappens M, Leutwyler S (1988) Molecular beams of clusters. In: Scoles G (ed) Atomic and molecular beam method, vol 1. Oxford University Press, New YorkGoogle Scholar
  4. 4.
    Smalley RE, Wharton L, Levy DH (1977) Molecular optical spectroscopy with supersonic beams and jets. Acc Chem Res 10:139–145CrossRefGoogle Scholar
  5. 5.
    Caldin FF, Gold V (1975) Proton-transfer reactions. Chapman and Hall, LondonGoogle Scholar
  6. 6.
    Mataga N, Kubota T (1970) Hydrogen bonding complexes. In: Molecular interactions and electronic spectra. Dekker, New York, pp 293–369Google Scholar
  7. 7.
    Cohen AO, Marcus RA (1968) Slope of free energy plots in chemical kinetics. J Phys Chem 72:4249–4256CrossRefGoogle Scholar
  8. 8.
    Lee J, Griffin RD, Robinson GW (1985) 2-Naphthol: A simple example of proton transfer effected by water structure. J Chem Phys 82:4920–4925CrossRefGoogle Scholar
  9. 9.
    Itoh M, Adachi T, Tokumura K (1984) Time-resolved fluorescence and absorption spectra and two-step laser excitation fluorescence of excited-state proton transfer in a methanol solution of 7-hydroxyquinoline, J Am Chem Soc 106:850–855CrossRefGoogle Scholar
  10. 10.
    Mukaihata H, Nakagawa T, Kohtani S, Itoh M (1994) Picosecond and two-step LIF studies of excite-state proton transfer in 3-hydroxyxanthone and 7-hydroxyflavone methanol solutions: Reinvestitation of tautomer and anion formations. J Am Chem Soc 116:10612–10618CrossRefGoogle Scholar
  11. 11.
    Kasha M (1986) Proton-transfer spectroscopy. J Chem Soc, Faraday Trans 82:2378–2392Google Scholar
  12. 12.
    Barbara PF, Walsh PK, Brus LE (1989) Picosecond kinetics and vibrationally resolved spectroscopic studies of intramolecular excited-state hydrogen atom transfer. J Phys Chem 93:29–34CrossRefGoogle Scholar
  13. 13.
    Fuke K, Yoshiuchi H, Kaya K (1984) Electronic spectra and tautomerism of hydrogen-bonded complexes of 7-azaindole in a supersonic jet. J Phys Chem 88:5840–5844CrossRefGoogle Scholar
  14. 14.
    Tokumura K, Watanabe Y, Udagawa M, Itoh M (1987) Photochemistry of a transient tautomer of the 7-azaindole H-bonded dimer studied by two-step laser excitation fluorescence measurements. J Am Chem Soc 109:1346–1350CrossRefGoogle Scholar
  15. 15.
    Fuke K, Tsukamoto K, Misaizu F, Kaya K (1991) Picosecond measurements of the vibrationally resolved proton transfer rate of the jet-cooled 1-azacarbazole dimer. J Chem Phys 95:4074–4080CrossRefGoogle Scholar
  16. 16.
    Fuke K, Kaya K (1989) Dynamics of double-proton-transfer reaction in the excited-state model hydrogen-bonded base pairs. J Phys Chem 93:614–621CrossRefGoogle Scholar
  17. 17.
    Alves ACP, Hollas JM (1973) Near-ultraviolet absortion spectrum of tropolone vapor: II Vibrational analysis. Mol Phys 25:1305–1314CrossRefGoogle Scholar
  18. 18.
    Tomioka Y, Ito M, Mikami N (1983) Electronic spectra of tropolone in a supersonic free jet. Proton tunneling in the S1 state. J Phys Chem 87:4401–4405CrossRefGoogle Scholar
  19. 19.
    Felker PM, Lambert WR, Zewail AH (1982) Picosecond excitation of jet-cooled hydrogen-bonded systems: Dispersed fluorescence and time-resolved studies of methyl salicylate. J Chem Phys 77:1603–1605CrossRefGoogle Scholar
  20. 20.
    Wiechmann M, Port H, Frey W, Larmer F, Elsasser T (1991) Time-resolved spectroscopy on ultrafast proton transfer in 2-(2′-hydroxy-5′-methylphenyl)benzotriazole in liquid and polymer environments. J Phys Chem 95:1918–1923CrossRefGoogle Scholar
  21. 21.
    Fujiwara Y, Itoh M (1985) Transient absorption and two-step laser excitation fluorescence studies of photoisomerization in 2-(2-hydroxyphenyl)benzoxazole and 2-(2-hydroxyphenyl)benzothiazole. J Am Chem Soc 107:1561–1565CrossRefGoogle Scholar
  22. 22.
    Becker RS, Lenoble C, Zein A (1988) A comprehensive investigation of the photophysics and photochemistry of salicylideneaniline and derivatives of phenylbenzothiazole, including solvent effects. J Phys Chem 91:3509–3517CrossRefGoogle Scholar
  23. 23.
    Yuzawa T, Takahashi H, Hamaguchi H (1993) Submicrosecond time-resolved infrared study on the structure of photoinduced transient species of salicylideneaniline in acetonitrile. Chem Phys Lett 202:221–226CrossRefGoogle Scholar
  24. 24.
    Chou PT, Martinez NL, Studer SI (1991) Role of triplet states in the reverse proton transfer mechanism of 7-hydroxy-1-indanone. J Phys Chem 95:10306–10310CrossRefGoogle Scholar
  25. 25.
    Itoh M, Tokumura K, Tanimoto Y, Okada Y, Takeuchi H, Obi K, Tanaka I (1982) Time-resolved and steady-state fluorescence studies of excited-state proton transfer in 3-hydroxyflavone and 3-hydroxychromone. J Am Chem Soc 104:4146–4150CrossRefGoogle Scholar
  26. 26.
    Ito A, Fujiwara Y, Itoh M (1992) Intramolecular excited-state proton transfer in jet-cooled 2-substituted 3-hydroxychromones and their water clusters. J Chem Phys 96:7474–7482CrossRefGoogle Scholar
  27. 27.
    Itoh M, Fujiwara Y, Matsudo M, Higashikata A, Tokumura K (1990) Transient absorption and two-step laser-induced fluorescence studies of the intramolecular excited-state proton transfer and relaxation process in 2-naphthyl-3-hydroxychromones. J Phys Chem 94:8146–8152CrossRefGoogle Scholar
  28. 28.
    Itoh M, Yuzawa T, Mukaihata H, Hamaguchi H (1995) Time-resolved infrared study of the relaxation process of intramolecular excited-state proton transfer in 2-naphthyl-3-hydroxychromone. Chem Phys Lett 233:550–554CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Tokyo 1998

Authors and Affiliations

  • Michiya Itoh

There are no affiliations available

Personalised recommendations