Sterically Hindered Tetradentate [Pt(O^N^C^N)] Emitters with Radiative Decay Rates up to 5.3 × 10 5 s -1 for Phosphorescent Organic Light-Emitting Diodes with LT 95 Lifetime over 9200 h at 1000 cd m -2 .

Described here are sterically hindered tetradentate [Pt(O^N^C^N)] emitters (Pt-1, Pt-2, and Pt-3) developed for stable and high-performance green phosphorescent organic light-emitting diodes (OLEDs). These Pt(II) emitters exhibit strong saturated green phosphorescence (λ max = 517-531 nm) in toluene and mCP thin films with emission quantum yields as high as 0.97, radiative rate constants (k r ) as high as 4.4-5.3 × 10 5 s -1 and reduced excimer emission, and with a preferential horizontally oriented transition dipole ratio of up to 84%. Theoretical calculations show that p-(hetero)arene substituents at the periphery of the ligand scaffolds in Pt-1, Pt-2, and Pt-3 can i) enhance the spin-orbit coupling (SOC) between the lower singlet excited states and the T 1 state, and S 0 →S n (n = 1 or 2) transition dipole moment, and ii) introducing additional SOC activity and the bright 1 ILCT[π(carbazole)→π*(N^C^N)] excited state (Pt-2 and Pt-3), which are the main contributors to the increased k r values. Utilizing these tetradentate Pt(II) emitters, green phosphorescent OLEDs are fabricated with narrow-band electroluminescence (FWHM down to 36 nm), high external quantum efficiency, current efficiency up to 27.6% and 98.7 cd A -1 , and an unprecedented device lifetime (LT 95 ) of up to 9270 h at 1000 cd m -2 under laboratory conditions.