Effect of alkyl substituents on excited state intramolecular proton transfer dynamics of jet-cooled bis(benzoxazolyl)phenoles

Abstract

Structural factors affecting the dynamics of the excited state intramolecular proton transfer (ESIPT) are studied for alkyl derivatives of 2,5-bis(2-benzoxazolyl)phenol. Two fluorescence bands with equal decay times are observed in solution, while only one--emitted by the phototautomer--in supersonic jet. All evidence indicates the existence of a potential barrier in the S(1) state. Upon deuteration of the OH group the laser induced fluorescence (LIF) excitation spectra become much sharper as a result of slowing down the proton transfer reaction. Two conformers (rotamers) of each compound in the ground state were detected using hole burning technique. With a help of theoretical calculations three vibrations were identified as the most active ones in reducing the distance between two heavy atoms, N and O, involved in H-bond formation. The widths of (0,0) transitions in LIF excitation spectra decrease with increasing size or number of alkyl substituents at terminal aromatic rings. The corresponding calculated rate constants of ESIPT reaction ( approximately 10(12) s(-1)) decrease approximately three times upon the substituent effect. In contrast, model compound 2,5-bis(2-benzoxazolyl)-4-methoxyphenol (BBMP) with OCH(3) parasubstituent in central ring slows down the ESIPT reaction to such an extent that double, primary and phototautomeric, fluorescences coexist.