Abstract: Energy level alignment of frontier molecular orbital (FMO) is essential for controlling charge carrier and exciton dynamics in organic light-emitting diodes (OLEDs). However, multiple resonance (MR) emitters with exceptional narrowband luminescence typically suffer from inadequate FMO levels. Herein, a conventional blue MR prototype with a shallow highest occupied molecular orbital (HOMO) level of −5.32 eV is initially employed to reveal the charge carrier and exciton dynamics. Severe hole trapping by its shallow HOMO significantly hinders its transport. More importantly, trapped carriers induce direct exciton formation and recombination at MR emitters in a hyperfluorescent system, leading to triplet accumulation in MR emitters. To resolve these issues, a proof-of-concept wavefunction perturbation strategy is proposed by incorporating cyano motifs at peripheral sites of MR backbone to adjust the energy levels. This approach significantly shifts HOMOs of 0.36 and 0.51 eV without compromising colour purity. The derivative substituting meta-boron position (mCNDB) exhibits a pure-blue emission peaking at 459 nm with a narrow bandwidth of 13 nm. The detrimental carrier trapping effect is eliminated, enhancing external quantum efficiency to exceeding 23%, maintaining around 20% at 1000 cd m−2, and improving the device stability.
