Excited-State Modification of Phenylimidazole-Based Cyclometalated Ir(III) Complexes through Secondary Bulky Aryl Substitution and Inductive Modification Enhances the Blue Emission Efficiency in Phosphorescent OLEDs.

To elucidate the key parameters governing the emission properties of phenylimidazole (pim)-based Ir(III) emitters, including their electronic structure and the bulky aryl substitution effect, a series of pim-based iridium(III) complexes ( Ir( R pim-X) 3 , R pim-X = 1-R-2-(X-phenyl)-1 H -imidazole) bearing secondary pendants of increasing bulkiness [R = methyl (Me), phenyl (Ph), terphenyl (TPh), or 4-isopropyl terphenyl (ITPh)] and three different primary pim ligands (X = F, F 2 , and CN) were designed and synthesized. Based on photophysical and electrochemical analyses, it was found that the excited state properties are highly dependent on the bulkiness of the secondary substituent and the inductive nature of the primary pim ligand. The incorporation of bulky TPh/ITPh substituents in the second coordination sphere significantly enhanced the emission efficiencies in the solid state (Φ PL = 72.1-84.9%) compared to those of the methyl- or phenyl-substituted Ir(III) complexes (Φ PL = 30.4% for Ir( Me pim) 3 and 63.7% for Ir( Ph pim) 3 ). Further modification of the secondary aryl substituent ( Ir( TPh pim) 3 → Ir( ITPh pim) 3 ) through the incorporation of an isopropyl group and F substitution on the primary pim ligand ( Ir( TPh/ITPh pim) 3 → Ir( TPh/ITPh pim-F/F 2 ) 3 ) resulted in a slight decrease in the LUMO and a significant decrease in the HOMO energy levels, respectively; these energy level adjustments consequently amplified emission blue shifts, thereby enabling efficient blue electroluminescence in phosphorescent organic light-emitting diodes. Theoretical calculations revealed that the excited-state properties of pim-based Ir(III) complexes can be modulated by the nature of the peripheral substituent and the presence of an EWG substituent. Among the fabricated blue-emitting TPh/ITPh-substituted Ir(III) complexes, Ir( ITPh pim-F) 3 , Ir( TPh pim-F 2 ) 3 , and Ir( ITPh pim-F 2 ) 3 were tested as blue-emitting dopants for blue phosphorescent OLEDs owing to their high solid radiative quantum yields (Φ PL = 75.9-84.9%). The Ir( ITPh pim-F) 3 -doped multilayer device displayed the best performance with a maximum external quantum efficiency of 21.0%, a maximum current efficiency of 43.6 cd/A, and CIE coordinates of 0.18 and 0.31.