Excited-state intramolecular proton transfer in 2-(2′-aminophenyl) benzimidazole Original Research Article

An excited-state intramolecular proton transfer process has been studied in 2-(2′-aminophenyl)benzimidazole (2-APBI) in different solvents using steady state and time resolved fluorescence spectroscopy. Semi-empirical quantum mechanical calculations (AM1 and CNDO/S-CI) have also been carried out. Dual fluorescence (normal and tautomer fluorescence) is observed in non-polar solvents. Based on the fluorescence excitation spectra recorded at different wavelengths, it is concluded that the normal fluorescence originates from rotamer II or IV and tautomer fluorescence from rotamer V. The tautomer fluorescence intensity decreases with increase in the polarity and hydrogen bonding capacity of the solvents. Different fluorescence lifetimes of the normal and tautomer bands indicate that rotamer I and II are not in equilibrium in the excited state. Semi-empirical quantum mechanical calculations have shown that the rotamer II is slightly more stable than the rotamer I in the ground state whereas in polar solvents, the stability of rotamer II increases due to extra solvation. For isolated molecule the activation energy for the interconversion of rotamers is 2.71 kJ mol−1 in the ground state, whereas it is 36 kJ mol−1 in the first excited singlet state.