Effects of substituted chalcogen atoms on excited state proton transfer reaction for 2,5‐bis(benzoxazole‐2‐yl)‐thiophene‐3,4‐diol derivatives: A theoretical study

Abstract Motivated by the captivating allure of exquisitely regulated characteristics exhibited by 2‐(2‐hydroxyphenyl)‐benzoxazole and its derivatives in the domains of photochemistry and photophysics, our current endeavor primarily focuses on delving into the intricacies of photo‐induced excited state reactions for derivatives of 2,5‐bis(benzoxazol‐2‐yl)‐thiophene‐3,4‐diol (BTD). Given the profound impact of chalcogen element doping, our primary focus lies in investigating the excited state behaviors of BTD‐O, BTD‐S, and BTD‐Se fluorophores. Through simulations encompassing variations in geometry and vertical excitation charge reorganization, we unveil atomic‐electronegativity‐dependent hydrogen bonding interactions and photoexcitation‐induced charge recombination that can significantly augment the intramolecular double proton transfer (ESDPT) reaction in the excited state for BTD‐O, BTD‐S, and BTD‐Se fluorophores. By constructing potential energy surfaces and identifying transition state forms, we elucidate the ultrafast stepwise ESDPT mechanism facilitated by the low potential barriers. Moreover, we rigorously validate the chalcogen atomic electronegativity‐driven regulation of the stepwise ESDPT mechanism. We sincerely anticipate that manipulating solvent polarity will pave the way for groundbreaking advancements in luminescent materials.