Theoretical uncovering of the chalcogen element regulated ESDPT behaviors for 2,5-bis(2-benzoxazolyl)-hydroquinone derivatives.

Inspired by the captivating allure of exquisitely regulated characteristics exhibited by 2-(2-hydroxyphenyl)-benzoxazole and its derivatives in the realms of photochemistry and photophysics, our current endeavor primarily revolves around delving into the intricacies of photo-induced excited state reactions for derivatives of 2,5-bis(2-benzoxazolyl)-hydroquinone (BBHQ). Given the significant impact of chalcogen element doping, herein we predominantly focus on exploring the excited state behaviors of BBHQ-OO, BBHQ-SS, and BBHQ-SeSe fluorophores. Our simulations, resulting from variations in geometry and vertical excitation charge reorganization, reveal atomic-electronegativity-dependent hydrogen bonding interactions and charge recombination induced by photoexcitation that can significantly enhance the excited state intramolecular double proton transfer (ESDPT) reaction for BBHQ-OO, BBHQ-SS, and BBHQ-SeSe fluorophores. By constructing potential energy surfaces (PESs) and identifying transition states (TS), we unveil the ultrafast stepwise ESDPT mechanism due to the low potential barriers. Additionally, by employing heterosubstituted BBHQ-OS and BBHQ-OSe compounds, we rigorously validate the stepwise ESDPT mechanism regulated by chalcogen atomic electronegativity. We sincerely anticipate that the modulation of solvent polarity on excited state behaviors will pave the way for groundbreaking advancements in luminescent materials.