Enhancing Spin–Orbit Coupling in an Indolocarbazole Multiresonance Emitter by a Sulfur-Containing Peripheral Substituent for a Fast Reverse Intersystem Crossing

A fast reverse intersystem crossing (RISC) remains an ongoing pursuit for multiresonance (MR) emitters but faces formidable challenges, particularly for indolocarbazole (ICz) derived ones. Here, heavy-atom effect is introduced first to construct ICz-MR emitter using a sulfur-containing substitute, simultaneously enhancing both spin–orbit and spin–vibronic coupling to afford a fast RISC with a rate of 1.2 × 10⁵ s⁻¹, nearly one order of magnitude higher than previous maximum values. The emitter also exhibits an extremely narrow deep-blue emission peaking at 456 nm with full-width at half-maxima of merely 12 nm and a photoluminescence quantum yield of 92%. Benefiting from its efficient triplet upconversion capability, this emitter achieves not only a high maximum external quantum efficiency (EQE) of 31.1% in organic light-emitting diodes but also greatly alleviates efficiency roll-off, affording record-high EQEs of 29.9% at 1000 cd m⁻² and 18.7% at 5000 cd m⁻² among devices with ICz-MR emitters.