Elevating the upconversion performance of a multiple resonance thermally activated delayed fluorescence emitter via an embedded azepine approach

Abstract

Multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters hold promise for efficient organic light-emitting diodes (OLEDs) and wide gamut displays. An azepine donor is introduced into the boron–nitrogen system for the first time. The highly twisted conformation of a seven-ring embedded new molecule, TAzBN, increases the intermolecular distances, suppressing self-aggregation emission quenching. Meanwhile, the azepine donor is crucial to achieve a narrow singlet-triplet gap (0.03 eV) as well as boost the reverse intersystem crossing (RISC) rate to 8.50 × 10⁵ s⁻¹. It is noteworthy that TAzBN demonstrates an impressive photoluminescence quantum yield of 94%. In addition, its nonsensitized OLED displayed a remarkable external quantum efficiency (EQE_max) with values peaking at 27.3%, and an EQE of 21.4% at 500 cd m⁻². This finding shows that when TAzBN is used at a high concentration of 10 wt%, its device maintains efficiency even at higher brightness levels, highlighting TAzBN's resistance to aggregation quenching. Furthermore, TAzBN enantiomers showed circularly polarized photoluminescence characteristics with dissymmetry factors |g_PL| of up to 1.07 × 10⁻³ in doped films. The curved heptagonal geometry opens an avenue to design the MR-TADF emitters with fast spin-flip and chiroptical properties.