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, (pzptBphFO)­H2, [(phpyim)­H2·(PF6)], and [(pimb)­H3·(PF6)2], which possess one dianionic pzptBphFO, together
with a second monoanionic tridentate chelate, namely, (pzptBphFO)­H, phpyim, and pimb, respectively. Moreover, a homoleptic,
charge-neutral complex 2 was obtained by methylation
of chelating (pzptBphFO)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 CIEx,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.