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Excited State Lactim to Lactam Type Tautomerization Reaction in 5-(4-Fluorophenyl)-2-Hydroxypyridine: Spectroscopic Study and Quantum Chemical Calculation

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Abstract

The photophysical properties of 5-(4-fluorophenyl)-2-hydroxypyridine (FP2HP) have been studied by steady state and time resolved spectroscopy in combination with quantum chemical calculations. The molecule FP2HP exists as lactim and lactam form in the ground state due to small stability difference but does not undergo lactim to lactam isomerisation due to high barrier energy. Whereas in the excited state the lactim form undergoes tautomerization producing red shifted emission of the lactam tautomer along with the local emission of the lactim form. In polar protic solvents, the barrier for lactim-lactam tautomerization rapidly decreases forming the lactam tautomer only. Temperature has pronounced effect on the excited state tautomerization equilibrium and is clearly reflected in the measured equilibrium constant (K 0tau ) and free energy change (ΔG0). Structural calculations at Hartree Fock and Density Functional Theory levels, calculated stability of the isomers in different solvents using Polarized Continuum Model and the theoretical potential energy surfaces for the ground and excited states along the proton transfer coordinate are reported for the tautomeric equilibrium of FP2HP.

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Acknowledgement

NG acknowledges DST, India (Project No. Project No. SR/S1/PC/26/2008) and CSIR, India (Project no. 01(2161)07/EMR-II) for financial support and AS and BKP thanks CSIR, New Delhi, for Senior Research Fellowship. The authors are thankful to Dr. Nitin Chattopadhyay of Jadavpur University, Kolkata, for allowing them to use fluorescence lifetime measurement set-up.

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  1. Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata, 700009, India

    Anuva Samanta, Bijan Kumar Paul, Samiran Kar & Nikhil Guchhait

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  1. Anuva Samanta
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  2. Bijan Kumar Paul
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  3. Samiran Kar
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  4. Nikhil Guchhait
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Correspondence to Nikhil Guchhait.

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Samanta, A., Paul, B.K., Kar, S. et al. Excited State Lactim to Lactam Type Tautomerization Reaction in 5-(4-Fluorophenyl)-2-Hydroxypyridine: Spectroscopic Study and Quantum Chemical Calculation. J Fluoresc 21, 95–104 (2011). https://doi.org/10.1007/s10895-010-0692-3

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  • DOI: https://doi.org/10.1007/s10895-010-0692-3

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