Roles of Ancillary Chelates and Overall Charges of Bis-tridentate Ir(III) Phosphors for OLED Applications

A series of charge-neutral bis-tridentate Ir­(III) complexes (1, 3, and 4) were prepared via employing three distinctive tridentate prochelates, that is, (pzp^tBph^FO)­H₂, [(phpyim)­H₂·(PF₆)], and [(pimb)­H₃·(PF₆)₂], which possess one dianionic pzp^tBph^FO, together with a second monoanionic tridentate chelate, namely, (pzp^tBph^FO)­H, phpyim, and pimb, respectively. Moreover, a homoleptic, charge-neutral complex 2 was obtained by methylation of chelating (pzp^tBph^FO)H of 1 in basic media, while closely related cationic complexes 5–7 were obtained by further methylation of the remaining pyrazolate unit of previously mentioned neutral complexes 2–4, followed by anion metatheses. All of these Ir­(III) metal complexes showed a broadened emission profile with an onset at ∼450 nm, a result of an enlarged ligand-centered ππ* transition gap, but with distinct efficiencies ranging from 0.8% to nearly unity. Comprehensive spectroscopic and computational approaches were executed, providing a correlation for the emission efficiencies versus energy gaps and between the metal-to-ligand charge transfer/ππ* emitting excited state and upper-lying metal-centered dd quenching state. Furthermore, Ir­(III) complexes 3 and 4 were selected as dopant emitters in the fabrication of sky-blue phosphorescent organic light-emitting diodes, affording maximum external quantum efficiencies of 16.7 and 14.6% with CIE_x,y coordinates of (0.214, 0.454) and (0.191, 0.404) at a current density of 10² cd/m², respectively. Hence, this research highlights an inherent character of bis-tridentate Ir­(III) complexes in achieving high phosphorescence quantum yield at the molecular level.