Deciphering the Mechanism of Aggregation-Induced Emission of a Quinazolinone Derivative Displaying Excited-State Intramolecular Proton-Transfer Properties: A QM, QM/MM, and MD Study

A combination of excited-state intramolecular proton transfer (ESIPT) and aggregation-induced emission (AIE) has opened new opportunities to develop color-tunable luminescent materials with high quantum yield. Understanding the emission mechanism of these luminophores is essential for the molecular design and construction of a functional system. Herein, we report QM (MS-CASPT2//TD-DFT, MS-CASPT2//CASSCF) and ONIOM (QM/MM) studies on the fluorescence quenching and AIE mechanisms of 2-(2-hydroxy-phenyl)-4­(3H)-quinazolinone with typical characteristics of AIE and ESIPT as an example. The computational results indicate that in the tetrahydrofuran solution, once being excited to the S1 state, the molecule tends to undergo an ultrafast, barrierless ESIPT from enol to keto tautomer and then accesses a S1/S0 conical intersection in the vicinity of a CC bond twisted intramolecular charge-transfer (TICT) intermediate, leading to a nonradiative decay from the excited to ground state. Hence, the TICT-induced nonadiabatic transition, which has been further confirmed by the on-the-fly trajectory surface hopping dynamics simulations, accounts for the fluorescence quenching in solution. In contrast, in the solid state, the nonradiative relaxation pathway via the CC bond rotation is suppressed due to environmental hindrance, leaving the ESIPT-induced enol–keto tautomerization as the only excited-decay channel, thus the fluorescence is observably enhanced in the crystal.