Mechanical Insights into Aggregation‐Induced Delayed Fluorescence Materials with Anti‐Kasha Behavior

Organic materials with aggregation‐induced delayed fluorescence (AIDF) have exhibited impressive merits for improving electroluminescence efficiency and decreasing efficiency roll‐off of nondoped organic light‐emitting diodes (OLEDs). However, the lack of comprehensive insights into the underlying mechanism may impede further development and application of AIDF materials. Herein, AIDF materials consisting of benzoyl serving as an electron acceptor, and phenoxazine and fluorene derivatives as electron donors are reported. They display greatly enhanced fluorescence with increased delayed component upon aggregate formation. Experimental and theoretical investigations reveal that this AIDF phenomenon can be rationally ascribed to the suppression of internal conversion and the promotion of intersystem crossing in solid. Moreover, the theoretical calculations disclose that the efficient solid‐state delayed fluorescence originates from the higher energy electronic excited state (e.g., S(2)) rather than the lowest energy‐excited state (S(1)), demonstrating an anti‐Kasha behavior. The excellent AIDF property allows high exciton utilization and thus superb performance of OLEDs using these new materials as light‐emitting layers.