Phosphorescent dopants are promising candidates for organic light‐emitting diodes (OLEDs). Although it has been established that the out‐coupling efficiency and overall performances of vacuum‐deposited OLEDs can be significantly improved by a horizontal orientation of the dopants, no horizontally oriented gold(III) complexes have been reported to date. Herein, a novel class of tetradentate C^C^N^N ligand‐containing gold(III) complexes with a preferential horizontal orientation successfully generated through a one‐pot reaction is reported. These complexes demonstrate high photoluminescence quantum yields of 70 % and a high horizontal dipole ratio of 0.87 in solid‐state thin films. Green‐emitting OLEDs based on these complexes operate with a maximum external quantum efficiency of 20.6 % with an estimated out‐coupling efficiency of around 30 %. A promising device stability has been achieved in the vacuum‐deposited OLEDs, with operational half‐lifetimes of around 37 500 h at 100 cd m−2.

Switch on of TADF can be achieved by tuning the excited state energy levels via ligand manipulation of the carbazolylgold(iii) C^C^N complexes. The resulting OLEDs show maximum EQEs of over 11% and efficiency roll-offs of down to less than 1%.

A new series of robust C^C^N carbazolylgold(III) complexes is designed and synthesized through the introduction of inert and sterically bulky oligophenyl substituents on the pyridyl moiety of the cyclometalating ligand. High photoluminescence quantum yields of up to 96% are recorded with these complexes doped in solid-state thin films, and short excited-state lifetimes of 0.3 μs or less in the solid state at room temperature are found. Promising electroluminescence (EL) performances are shown by the vacuum-deposited organic light-emitting devices (OLEDs) based on this series of gold(III) complexes. High external quantum efficiencies of up to 19.5% with efficiency roll-offs of down to 10% at a practical luminance brightness level of 1000 cd m −2 are achieved. More importantly, record-long operational lifetimes (LT 50 ) of up to 470,700 h at 100 cd m −2 are realized, which is currently the highest value among all classes of gold(III) complexes with tridentate pincer ligands. Particularly, by introducing a sterically bulky terphenyl moiety on the reactive site of the pyridine ring, the LT 50 value is shown to attain ∼7 times longer half-lifetime than that based on the unsubstituted complex. These unprecedented EL performances and the simple synthetic route in a mercury-free fashion make them promising emitting materials for practical OLEDs toward commercialization.