Novel U-shaped donor–acceptor–donor (D–A–D) π-conjugated multi-functional molecules comprising dibenzo[a,j]phenazine (DBPHZ) as an acceptor and phenothiazines (PTZ) as donors have been developed. Most importantly, the D–A–D compounds exhibit not only distinct tricolor-changeable mechanochromic luminescence (MCL) properties but also efficient thermally activated delayed fluorescence (TADF). Quantum chemical calculations, X-ray diffraction analysis, and systematic studies on the photophysical properties indicated that the “two-conformation-switchable” PTZ units play a highly important role in achieving multi-color-changing MCL. Time-resolved photophysical measurements revealed that the developed D–A–D compounds also exhibit efficient orange-TADF. Furthermore, organic light-emitting diode (OLED) devices fabricated with the new TADF emitters have achieved high external quantum efficiencies (EQEs) up to 16.8%, which significantly exceeds the theoretical maximum (∼5%) of conventional fluorescent emitters.

A new class of thermally activated delayed fluorescent donor–acceptor–donor–acceptor (D–A–D–A) π-conjugated macrocycle comprised of two U-shaped electron-acceptors (dibenzo[a,j]phenazine) and two electron-donors (N,N’-diphenyl-p-phenyelendiamine) has been rationally designed and successfully synthesized. The macrocyclic compound displayed polymorphs-dependent conformations and emission properties. Comparative studies on physicochemical properties of the macrocycle with a linear surrogate has revealed significant effects of the structural cyclization of D–A-repeating structure, including more efficient thermally activated delayed fluorescence (TADF). Furthermore, an organic light-emitting diode (OLED) device fabricated with the macrocycle compound as the emitter has achieved a high external quantum efficiency (EQE) up to 11.6%, far exceeding the theoretical maximum (5%) of conventional fluorescent emitters and that with linear analog (6.9%).

Organic emitting compounds that are based on π‐conjugated skeletons have emerged as promising next‐generation materials for application in optoelectronic devices. In this Minireview, recent advances in the development of organic emitters that irradiate room‐temperature phosphorescence and/or thermally activated delayed fluorescence with extraordinary luminescence properties, such as aggregation‐induced emission, mechanochromic luminescence, and circularly polarized luminescence, are discussed.