Delocalized Nonbonding Orbitals of Thioxanthone in Polycyclic Aromatic Hydrocarbons for Reduced Energy Gap and Narrowband Emission

Chalcogen‐containing carbonyls, specifically thioxanthone (TX), hold great potential in organic light‐emitting diodes (OLEDs). While the development of narrowband OLEDs with chalcogen‐containing carbonyls remains challenging due to difficulties in achieving both high device efficiency and narrow emission spectra. Herein, via a strategic incorporation of the TX moiety, two orange‐red narrowband emitters, 2TXBN and BNTXBN, are designed and synthesized for the first time. Both 2TXBN and BNTXBN exhibit bright orange‐red emissions with peaks at 582 and 585 nm, respectively, along with narrow full widths at half maximum of 30 and 32 nm. Notably, 2TXBN demonstrates delocalization of the nonbonding orbital within the TX segment, which raises the first triplet energy level and reduces the singlet‐triplet energy gap. This electronic structural adjustment effectively shortens the delayed fluorescence lifetime, leading to enhanced device performance. Accordingly, OLED employing 2TXBN as the emitter achieves remarkable performance, with a maximum external quantum efficiency of 31.0%, a current efficiency of 69.0 cd A‐1, and a power efficiency of 76.0 lm W‐1, highlighting the efficacy of the nonbonding orbital delocalization strategy in achieving bathochromic‐shifted narrowband OLED materials.