Exploring and Regulating Heteroatom-Electronegativity-Associated with Ring Aromaticity and Excited State Intramolecular Proton Transfer Mechanism for Benzothiazole-Based Fluorophore

A novel fluorophore 2-(2'-hydroxy-5'-benzaldehyde phenyl) benzothiazole (HBBT) with excited state intramolecular proton transfer (ESIPT) characteristics, showing good selectivity for Cu⁺/Cu²⁺ ions had been synthesized experimentally (<i>Molecules</i> 2022, 27, 7678). However, its ESIPT mechanism and fluorescent performance related to atomic substituents have not been investigated systematically. In this work, two HBBT derivatives, 2-(2'-hydroxy-5'-benzaldehyde phenyl)benzoimidazole (HBBI) and 2-(2'-hydroxy-5'-benzaldehyde phenyl)benzopyrrole (HBBP), were obtained by respectively using -NH and -CH₂ groups in place of the sulfur atom in the thiazole ring. The absorption/emission spectra and ring aromaticity as well as ESIPT processes of HBBT and its derivatives were studied using density functional theory (DFT) and time-dependent DFT (TD-DFT). The simulated absorption and fluorescence wavelengths of HBBT agreed well with the corresponding values obtained in the experiment. According to the analyses of geometry structures, electron densities, and infrared vibration frequencies, the intramolecular hydrogen bond becomes stronger upon light excitation. The frontier molecular orbitals were analyzed via establishing potential energy curves, and the ESIPT behavior was described deeply. Obviously, the NH-substitution makes ring 4 more aromatic, while the CH₂-substitution changes ring 4 from aromatic to antiaromatic. The ESIPT process helps to alleviate the excited state antiaromaticity. The greater the antiaromaticity of the S₁ state normal form, the higher the barrier of ESIPT.