Aggregation‐Dependent Thermally Activated Delayed Fluorescence Emitters: AIE or ACQ?

Abstract The understanding of the excited state dynamics of thermally activated delayed fluorescence (TADF) materials is crucial. In this study, two donor–acceptor‐type TADF emitters with highly twisted conformation are synthesized. The emitters with subtle chemical modification of donor unit exhibit opposite aggregation luminescent behaviors: aggregation‐induced emission (AIE) and aggregation‐caused quenching (ACQ). Through the photophysical properties study, crystallographic analysis, and theory simulations, it is discovered that X‐aggregation supports AIE behavior by restricting the intramolecular motions and preserving TADF emission via an efficient reverse intersystem crossing (RISC) process, but on the other hand, H‐aggregation leads to ACQ behavior due to inhibited RISC, disabled TADF channel, and weak phosphorescence from radiative low‐lying triplet state. The findings shed light on the excited‐state dynamic behaviors of TADF emitters, which are dependent on aggregation.