Clar's Aromatic π‐Sextet Rule for the Construction of Red Multiple Resonance Emitter

Abstract Despite the proliferation of multiple resonance (MR) materials in the blue to green spectral ranges, red MR emitters remain scarce in the literature, an area that certainly warrants attention for future applications. Here, through a clever application of classic Clar's aromatic π‐sextet rule, we triumphantly constructed the first red MR emitter by substituting the conventional benzene ring core with anthracene (fewer π‐sextets). Theoretical studies indicate that the quantity of π‐sextets ultimately determines the optical band gap of a molecule, rather than the number of fused benzene rings. Benefiting from the high photoluminescence quantum yield of ~94 % and horizontal dipole ratio of ~90 %, the corresponding narrowband red (luminescence wavelength: 608 nm) organic light‐emitting diode shows a high external quantum efficiency of 27.3 %, with only a slight decrease of 3.7 % at an elevated luminance level of 100,000 cd/m 2 .