Exploring Solvent Effects on the Proton Transfer Processes of Selected Benzoxazole Derivatives by Femtosecond Time-Resolved Fluorescence and Transient Absorption Spectroscopies.

Abstract

Excited-state intramolecular proton transfer (ESIPT) is of great importance due to the large Stokes shift emission that can be observed in some ESIPT molecules. Although steady-state spectroscopies have been employed to study the properties of some ESIPT molecules, their excited-state dynamics have not been examined directly with time-resolved spectroscopy methods yet for a number of systems. Here, an in-depth investigation of the solvent effects on the excited-state dynamics of two prototypical ESIPT molecules, 2-(2'-hydroxyphenyl)-benzoxazole (HBO) and 2-(2'-hydroxynaphthalenyl)-benzoxazole (NAP), have been accomplished by using femtosecond time-resolved fluorescence and transient absorption spectroscopies. Solvent effects affect the excited-state dynamics of HBO more significantly than that of NAP. Particularly in the presence of water, the photodynamics pathways of HBO are changed, while only small changes can be found in NAP. An ultrafast ESIPT process that occurs within our instrumental response is observed for HBO, and this is followed by an isomerization process in ACN solution. However, in aqueous solution, the obtained syn-keto* after ESIPT can be solvated by water in about 3.0 ps, and the isomerization process is totally inhibited for HBO. The mechanism of NAP is different from HBO and is determined to be a two-step excited-state proton transfer process. Upon photoexcitation, NAP is deprotonated first in the excited state to generate the anion*, which can transfer to the syn-keto* form followed by an isomerization process.