Extremely condensing triplet states of DPEPO-type hosts through constitutional isomerization for high-efficiency deep-blue thermally activated delayed fluorescence diodes

摘要

The similarity of thermally activated delayed fluorescence (TADF) dyes and their hosts as pure organic molecules makes hosts predominant in intermolecular interactions and crucial to exciton harvesting and utilization in TADF diodes. >DPEPO is the most popular high-energy-gap blue TADF host with steric ortho-substituted diphenylphosphine oxide (DPPO) groups for intermolecular interaction suppression, but suffers from serious efficiency roll-off due to its weak electroactivity. On the contrary, para-substituted DPPO with small steric hindrance is superior in intramolecular electronic coupling. In this work, four constitutional isomers of >DPEPO are constructed as diphenylether (>DPE) with two diphenylphosphine oxide (DPPO) groups substituted at either the 2 or 4 position, namely >22′DPEPO (viz.>DPEPO), >24DPEPO, >24′DPEPO and >44′DPEPO, respectively. On the basis of separation configuration, the steric effect and electroactivity of ortho- and para-substituted DPPOs are successfully integrated in >24′DPEPO, accompanied by remarkably reduced intermolecular interactions due to its unsymmetrical configuration. Compared to its congeners, >24′DPEPO has a rigid structure and locally excited states similar to >22′DPEPO for interaction suppression and improved charge mobility comparable to >44′DPEPO for charge flux balance. Significantly, by virtue of the predominant orientation effect of ortho-DPPO on the T1 location, its T1 state is extremely condensed onto a single phenyl, protected from intermolecular interactions by its remaining five phenyls at its maximum extent. Consequently, >24′DPEPO endowed its >DMAC-DPS-based deep-blue devices with state-of-the-art performance, including high color purity with chromaticity coordinates of (0.16, 0.17), external quantum efficiency (EQE) beyond 20% and EQE roll-off as low as 32% at 1000 cd m^–2. It is shown that the device performance of >24′DPEPO was far beyond simple integration of those of >22′DPEPO and >44′DPEPO, verifying the significance of host optimization.