Deep-Blue-Emitting Heteroleptic Iridium(III) Complexes Suited for Highly Efficient Phosphorescent OLEDs

We report on the design, synthesis, and characterization of four new heteroleptic iridium­(III) complexes bearing 2′,6′-difluoro-2,3′-bipyridine and pyridyl-azole ligands. The photophysical properties and cyclic voltammetry of the complexes were also investigated. All compounds display highly efficient genuine blue phosphorescence (λ_max ca. 440 nm), at room temperature in solution and in thin film, with quantum yield in the range 0.77–0.87 and 0.62–0.93, respectively. We found that introduction of the bulky <i>tert</i>-butyl substituents on the cyclometalated or azolated chelates can effectively reduce detrimental aggregation, which results in a loss of color purity. Comprehensive density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches have been performed on the ground and excited states of the here reported complexes, in order to gain deeper insights into their structural and electronic features as well as to ascertain the nature of the excited states involved into the electronic absorption processes. Moreover, electron spin density analysis and total electron density difference at the lowest-lying triplet state (T₁) were performed for shedding light onto the nature of the emitting excited state. Finally, the fabrication of the organic light-emitting diodes (OLEDs), employing the bulkiest derivative among the here reported phosphorescent dopants, was successfully made. The devices exhibit remarkable maximum external quantum efficiency (EQE) as high as 7.0%, in nonoptimized devices, and power efficiency (PE) of 4.14 lm W^–1, together with a true-blue chromaticity CIE_x,y = 0.159, 0.185 recorded at 300 cd m<sup>–2