Acid-Induced Shift of Intramolecular Hydrogen Bonding Responsible for Excited-State Intramolecular Proton Transfer

The significant progress recently achieved in designing smart acid-responsive materials based on intramolecular charge transfer inspired us to utilize excited-state intramolecular proton transfer (ESIPT) for developing a turn-on acid-responsive fluorescent system with an exceedingly large Stokes shift. Two ESIPT-active fluorophores, 2-(2-hydroxyphenyl)pyridine (HPP) and 2-(2-hydroxyphenyl)benzothiazole (HBT), were fused into a novel dye (HBT-HPP) fluorescent only in the protonated state. Moreover, we also synthesized three structurally relevant control compounds to compare their steady-state fluorescence spectra and optimized geometric structures in neutral and acidic media. The results suggest that the fluorescence turn-on was caused by the acid-induced shift of the ESIPT-responsible intramolecular hydrogen bond from the HPP to HBT moiety. This work presents a systematic comparison of the emission efficiencies and basicity of HBT and HPP for the first time, thereby utilizing their differences to construct an acid-responsive smart organic fluorescent material. As a practical application, red fluorescent letters can be written using the acid as an ink on polymer film.