Twist of C═C Bond Plays a Crucial Role in the Quenching of AIE-Active Tetraphenylethene Derivatives in Solution

Aggregation-induced emission (AIE) has emerged as a new class of attractive photoluminescence behavior. Understanding the precise mechanism of the AIE phenomenon will lead to the rational molecular design of novel molecules with AIE properties (AIEgens). In this work, we selected disubstituted derivatives of tetraphenylethene (TPE), a well-known archetypal AIEgen, as the model compounds to elucidate the AIE mechanism. As the result of photochemical experiments and quantum chemical computations, π-bond twist (π twist), including E–Z isomerization (EZI), was found to be the major factor for quenching the photoexcited state of TPE derivatives in the solution state, differently from the well-accepted propeller-like rotation of the side phenyl groups in earlier research. In photochemical experiments, the prepared TPE derivatives exhibited EZI in the solution state upon photoirradiation, and a negative correlation was observed between this isomerization and the AIE phenomenon. The theoretical computations verified the crucial role of π twist triggered by photoirradiation in the solution state, rather than intramolecular rotation. In the crystal state, π twist was efficiently suppressed by the surrounding molecules. Our results will support the realization of novel smart AIEgens that can respond to various external stimuli.