Journal of Fluorescence

, Volume 22, Issue 4, pp 1095–1100 | Cite as

Excited State Intramolecular Proton Transfer in O-Tosylaminobenzaldehyde

  • Mikhail N. Khimich
  • Leonid D. Popov
  • Anatoly S. Burlov
  • Boris M. Uzhinov
Original Paper

Abstract

Excited state intramolecular proton transfer (ESIPT) in o-tosylaminobenzaldehyde has been investigated. According to quantum-chemical calculations ESIPT in o-tosylaminobenzaldehyde is barrierless. Product of ESIPT undergoes efficient nonradiative deactivation caused by internal rotation of C(H)OH-group. The solvent orientational relaxation in anionic form of o-tosylaminobenzaldehyde was detected. The mechanism of anionic form fluorescence quenching at the addition of the base in a protic solvent is proposed. It consists in the intermolecular proton transfer from the protonated base to oxygen atom of aldehyde group followed by the internal rotation of C(H)OH-group.

Keywords

Fluorescence Proton transfer Internal rotation Relaxation 

References

  1. 1.
    Solntsev KM, Sullivan EN, Tolbert LM, Ashkenazi S, Leiderman P, Huppert D (2004) Excited-state proton transfer reactions of 10-hydroxycamptothecin. J Am Chem Soc 126:12701–12708. doi:10.1021/ja047821e PubMedCrossRefGoogle Scholar
  2. 2.
    Ushiyama H, Takatsuka K (2005) Methyl group rotation driven by proton transfer through a long-range chemical interaction. Angew Chem Int Ed 44:1237–1240. doi:10.1002/anie.200461459 CrossRefGoogle Scholar
  3. 3.
    Perez-Lustres JL, Rodriguez-Prieto F, Mosquers M, Senyushkina TA, Ernsting NP, Kovalenko SA (2007) Ultrafast proton transfer to solvent: molecularity and intermediates from solvation- and diffusion-controlled regimes. J Am Chem Soc 129:5408–5418. doi:10.1021/ja0664990 PubMedCrossRefGoogle Scholar
  4. 4.
    Chou PT (2001) The host/guest type of excited-state proton transfer in solution phase. J Chin Chem Soc 48:651–682Google Scholar
  5. 5.
    Parsapour F, Kelley DF (1996) Torsional and proton transfer dynamics in substituted 3-hydroxyflavones. J Phys Chem 100:2791–2798. doi:10.1021/jp9520106 CrossRefGoogle Scholar
  6. 6.
    Sytnik A, Kasha M (1994) Excited-state intramolecular proton transfer as a fluorescence probe for protein binding-site static polarity. Proc Natl Acad Sci USA 91:8627–8630PubMedCrossRefGoogle Scholar
  7. 7.
    Chou PT, McMorrow D, Aartsma TJ, Kasha M (1984) The proton-transfer laser. Gain spectrum and amplification of spontaneous emission of 3-hydroxyflavone. J Phys Chem 88:4596–4599. doi:10.1021/j150664a032 CrossRefGoogle Scholar
  8. 8.
    Acuña AU, Amat F, Catalán J, Costela A, Figuera JM, Muñoz JM (1986) Pulsed liquid lasers from proton transfer in the excited state. Chem Phys Lett 132:567–569. doi:10.1016/0009-2614(86)87126-3 CrossRefGoogle Scholar
  9. 9.
    Catalan J, del Valle JC, Claramunt RM, Sanz D, Dotor J (1996) Photophysics of the 2-(2′-hydroxyphenyl)perimidine: On the fluorescence of the enol form. J Lumin 68:165–170. doi:10.1016/0022-2313(96)00005-1 CrossRefGoogle Scholar
  10. 10.
    Roshal AD, Grigorovich AV, Doroshenko AO, Pivovarenko VG (1998) Flavonols and crown-flavonols as metal cation chelators. The different nature of Ba2+ and Mg2+ complexes. J Phys Chem A 102:5907–5914. doi:10.1021/jp972519w CrossRefGoogle Scholar
  11. 11.
    Scherl M, Harrer D, Fischer J, DeCian A, Lehn J-M, Eichen Y (1996) Proton-transfer processes in well-defined media: experimental investigation of photoinduced and thermal proton-transfer processes in single crystals of 2-(2,4-Dinitrobenzyl)pyridine derivatives. J Phys Chem 100:16175–16186. doi:10.1021/jp9609242 CrossRefGoogle Scholar
  12. 12.
    Klymchenko AS, Stoeckel H, Taneda K, Mely Y (2006) Fluorescent probe based on intramolecular proton transfer for fast ratiometric measurement of cellular transmembrane potential. J Phys Chem B 110:13624–13632. doi:10.1021/jp062385z PubMedCrossRefGoogle Scholar
  13. 13.
    Lochbrunner S, Stock K, Riedle E (2004) Direct observation of the nuclear motion during ultrafast intramolecular proton transfer. J Mol Struct 700:13–18. doi:10.1016/j.molstruc.2004.01.038 CrossRefGoogle Scholar
  14. 14.
    Chudoba C, Riedle E, Pfeiffer M, Elsaesser T (1996) Vibrational coherence in ultrafast excited state proton transfer. Chem Phys Lett 263:622–628. doi:10.1016/S0009-2614(96)01268-7 CrossRefGoogle Scholar
  15. 15.
    Neuwahl FVR, Foggi P, Brown RG (2000) Sub-picosecond and picosecond dynamics in the S1 state of [2,2′-bipyridyl]-3,3′-diol investigated by UV–visible transient absorption spectroscopy. Chem Phys Lett 319:157–163. doi:10.1016/S0009-2614(00)00099-3 CrossRefGoogle Scholar
  16. 16.
    Lochbrunner S, Wurzer AJ, Riedle E (2003) Microscopic mechanism of ultrafast excited-state intramolecular proton transfer: a 30-fs study of 2-(2′-Hydroxyphenyl)benzothiazole. J Phys Chem A 107:10580–10590. doi:10.1021/jp035203z CrossRefGoogle Scholar
  17. 17.
    Khimich MN, Gostev FE, Shelaev IV, Sarkisov OM, Birgen EA, Bolotin BM, Uzhinov BM (2010) Femtosecond dynamics of intramolecular photoinduced proton transfer in N-Substituted 2-(2-Aminophenyl)-4H-3,1-Benzoxazin-4-ones. High Energ Chem 44:482–491. doi:10.1134/S0018143910060056 CrossRefGoogle Scholar
  18. 18.
    Uzhinov BM, Khimich MN (2011) Conformational effects in excited state intramolecular proton transfer of organic compounds. Russ Chem Rev 80:553–577. doi:10.1070/RC2011v080n06ABEH004144 CrossRefGoogle Scholar
  19. 19.
    Chernova NI, Ryabokobylko VS, Brudz VG, Bolotin BM (1971) 2-tosylaminobenzaldehyde and its substituted derivatives. Zhurn organ Khim 7:1680–1687, russGoogle Scholar
  20. 20.
    Mahia J, Maestro M, Vazquez M, Bermejo MR, Gonzalez AM, Maneiro M (1999) 2-Tosylaminobenzaldehyde. Acta Crystallogr C 55:2158–2160. doi:10.1107/S0108270199011580 CrossRefGoogle Scholar
  21. 21.
    Weissberger A, Proskauer ES, Riddick JA, Toops EE (1955) Organic solvents physical properties and methods of purification. Interscience, New YorkGoogle Scholar
  22. 22.
    Melhuish WH (1961) Quantum efficiencies of fluorescence of organic substances: effect of solvent and concentration of the fluorescent solute. J Phys Chem 65:229–235. doi:10.1021/j100820a009 CrossRefGoogle Scholar
  23. 23.
    Granovsky AA (2011) Firefly version 7.1.G, www http://classic.chem.msu.su/gran/firefly/index.html
  24. 24.
    Granovsky AA (2011) Extended multi-configuration quasi-degenerate perturbation theory: the new approach to multi-state multi-reference perturbation theory. J Chem Phys 134:214113. doi:10.1063/1.3596699 PubMedCrossRefGoogle Scholar
  25. 25.
    Khimich MN, Volchkov VV, Uzhinov BM (2003) Fluorescence study of excited state relaxation processes of 2-pyridyl-5-aryloxazoles. J Fluor 13:301–306. doi:10.1023/A:1025321626680 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Mikhail N. Khimich
    • 1
  • Leonid D. Popov
    • 2
  • Anatoly S. Burlov
    • 3
  • Boris M. Uzhinov
    • 1
  1. 1.Chemistry DepartmentMoscow State UniversityMoscowRussia
  2. 2.Chemistry DepartmentSouthern Federal UniversityRostov-on-DonRussia
  3. 3.Institute of Physical and Organic ChemistrySouthern Federal UniversityRostov-on-DonRussia

Personalised recommendations