Rational Tuning of Bis-Tridentate Ir(III) Phosphors to Deep-Blue with High Efficiency and Sub-microsecond Lifetime

A new class of bis-tridentate Ir­(III) complexes (Dap-1–4) was synthesized using carbene pincer pro-chelates PC1·H3(PF6)2 or PC2·H3(PF6)2 with either imidazolylidene or imidazo­[4,5-b]­pyridin-2-ylidene appendages, together with a second cyclometalating 2,6-diaryoxypyridine chelate, L1H2 and L2H2, differed by a NMe2 donor at the central pyridinyl fragment. The respective emission tuning between the ultraviolet and blue region was rationalized using time-dependent density functional theory (TD-DFT) approaches. Next, a highly efficient blue emitter (Dap-5) was synthesized by concomitant addition of two methyl groups and a single CF3 substituent at the central phenyl and peripheral imidazo­[4,5-b]­pyridin-2-ylidene entities of the carbene pincer chelate, respectively. The organic light-emitting diode (OLED) device with 15 wt % Dap-5 in DPEPO shows electroluminescence at 468 nm and with CIE (0.14, 0.15) and a max external quantum efficiency (max EQE) of 16.8% with low efficiency roll-off (EQE of 14.4% at 1000 cd m–2); the latter is attributed to the relatively shortened triplet excited-state radiative lifetime. These results highlight the adequateness of bis-tridentate Ir­(III) phosphors in fabrication of practical blue-emitting OLEDs.