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Theoretical investigations of electronic structure and tautomerism in ground and excited states of 1-[N-(4-fluorophenyl)]naphthaldimine
Journal article

Theoretical investigations of electronic structure and tautomerism in ground and excited states of 1-[N-(4-fluorophenyl)]naphthaldimine

Nilesh R Dhumal and Shridhar P Gejji
Journal of molecular structure. Theochem, Vol.758(2), pp.259-262
2006

Abstract

Hybrid density functional Intramolecular excited state proton transfer Tautomers Time-dependent density functional
Electronic structure of 1-[ N-(4-Fluorophenyl)]naphthaldimine phenol-imine (1) and quinoid (2) tautomers in ground and excited states are presented. The density functional calculations predict the ground state of 1 to be 5.4 kJ mol −1 lower in energy owing to stronger O–H⋯N (1.638 Å) interactions relative to O⋯H–N (1.651 Å) interactions in 2. The influence of solvents on the tautomeric stability as revealed from the self-consistent reaction field (SCRF) calculations suggests tautomer 2 to be of lower energy in protic polar solvents. Time-dependent density functional (TDDFT) calculations on the other hand bring about the reversal of relative stabilization and facilitate the tautomer 2 to be 6.6 kJ mol −1 lower in energy in the lowest excited state which results from the extended conjugation owing to its planar geometry.

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