Excited State Intramolecular Proton Transfer and Charge Transfer Dynamics of a 2-(2′-Hydroxyphenyl)benzoxazole Derivative in Solution
journal contributionposted on 13.05.2010, 00:00 by Chul Hoon Kim, Jaehun Park, Jangwon Seo, Soo Young Park, Taiha Joo
Excited state intramolecular proton transfer (ESIPT) and subsequent intramolecular charge transfer (ICT) dynamics of a 2-(2′-hydroxyphenyl)benzoxazole derivative conjugated with an electron withdrawing group (HBOCE) in solutions and a polymer film has been investigated by femtosecond time-resolved fluorescence (TRF) and TRF spectra measurements without the conventional spectral reconstruction method. TRF with high enough resolution (<100 fs) reveals that the ESIPT dynamics of HBOCE in liquids proceeds by at least two time constants of ∼250 fs and ∼1.2 ps. The relative amplitude of the slower picosecond component is smaller in the polymer film than that in solution. Conformational heterogeneity in the ground state originating from the dispersion of the dihedral angle between the phenolic and benzoxazole groups is invoked to account for the dispersive ESIPT dynamics in liquids. From the TRF spectra of both the enol and keto isomers, we have identified the ICT reaction of the keto isomer occurring subsequent to the ESIPT. The ICT proceeds also by two time constants of near instantaneous and 2.7 ps. Since the ICT dynamics of HBOCE is rather close to the polar solvation dynamics, we argue that the ICT is barrierless and determined mostly by the solvent fluctuation.