Correlation between Excited-State Intramolecular Proton Transfer and Electron Population on Proton Donor/Acceptor in 2-(2′-Hydroxyphenyl)oxazole Derivatives

Modulating the excited-state intramolecular proton transfer (ESIPT) reaction to achieve anticipant performance is always fascinating for chemists. However, feasible methods and a definite mechanism for tuning the ESIPT reaction remain insufficient. In this work, we reported the feasibility of continuously modulating the ESIPT dynamics in 2-(2'-hydroxyphenyl)oxazole (HPO) derivatives with different substitutions on the positions 5 and 5' of the core HPO through steady-state/transient spectroscopy and theoretical calculations. We found that the main factor affecting the tendency of the ESIPT reaction is the variation of electron population on proton donor and acceptor. An index Δpdif was proposed to evaluate the overall promotion effect on proton transfer caused by the variation of electron population on proton donor and acceptor, which shows high reliability in interpreting the ESIPT tendency. This method, for its capacity to quickly estimate the tendency of ESIPT, shows great potential in ESIPT molecular design with chemical substitution of electron-donating/withdrawing moieties.