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

Abstract

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 T_<i>n</i> (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 (<i>k</i>_hRISC) 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.