Azepination-Induced Frontier Molecular Orbital Delocalization of Multiple Resonance Emitters: Constructing Highly Efficient Narrowband Electroluminescent Materials

Developing diversified construction strategies for high-color-purity and efficient multiple resonance thermally activated delayed fluorescence (MR-TADF) materials is a major strategic demand to meet the requirements of ultra-high-definition organic light-emitting diode (OLED) displays, posing a significant challenge to the design and synthesis of emitters at the molecular level. Herein, we propose a strategy for azepination-induced frontier molecular orbital (FMO) delocalization of MR emitters, that is, embedding azepine into the prototype molecule BNCz can effectively improve the π-conjugation degree and extend the FMO delocalization, thereby constructing a series of long-wavelength MR-TADF materials with narrowband emission. Through an intramolecular Scholl reaction, these target molecules with an azepine-embedded core are afforded by one-fold heptagonal cyclization of BNCz core and the phenyl ring attached to (aromatic amine-substituted) aryl precursor. They all exhibit efficient green emission around 520 nm and narrow full-widths at half-maximum (FWHMs) of ≤ 38 nm in toluene. OLEDs employing these emitters show excellent electroluminescence (EL) performances, among which m-PAz-BNCz-based OLED exhibits the optimal EL performances with a peak of 528 nm, a FWHM of 37 nm, Commission Internationale de L’Eclairage (CIE) coordinates of (0.26, 0.70), and a maximum external quantum efficiency (EQE) of 36.2%.