LAUSR

Novel homoleptic cyclometalated Ir(III) complexes are designed to improve their emission dipole orientations in the emitting layer of blue phosphorescent organic light emitting devices. Biphenyl group is introduced into the imidazole of cyclometalated Ir(III) complexes to simultaneously achieve enhanced efficiency and operation lifetime, resulting in one of the best device performances of single‐stacked organic light emitting diodes with 91% emission dipole orientation, 26.3% maximum external quantum efficiency (maximally calculated as 41%), and 169 h lifetime at 1000 cd m−2 (LT80), color coordinate (0.17, 0.30). To elucidate the physical origin of this significant improvements, the orientational and positional distributions of the homoleptic dopants are analyzed with consideration on intermolecular interactions through atomistic modeling of the emitting layer. With the findings, the phosphorescent dopants could be designed in the future to achieve enhanced performance.