Fine Modulation of the Higher-Order Excitonic States toward More Efficient Conversion from Upper-Level Triplet to Singlet

Hot exciton luminogens capable of harvesting nonemissive triplet excitons via reverse intersystem crossing from high-order triplet (hRISC) to singlet have great potential in high-efficiency fluorescent organic light-emitting diodes (OLEDs). Although spin–orbit coupling (SOC) is regarded as a key factor affecting the RISC process, its effects on hot exciton materials are poorly understood. Herein, we design and synthesize two blue-emitting hot exciton luminogens, PABP and PAIDO, to study this issue by modulating the excited-state properties. Theoretical and experimental research contributions demonstrate that a stronger SOC between energetically close S1 (π–π*) and Tn (T3, n−π*) of PAIDO gives rise to faster and more efficient hRISC in comparison to that of PABP, leading to a higher external quantum efficiency and a higher exciton utilization efficiency. Crucially, the experimentally measured hRISC rate (khRISC) of hot exciton materials is on the order of 107 s–1, which is much faster than that of the thermally activated delayed fluorescence materials.