A new class of four‐coordinate donor‐acceptor fluoroboron‐containing thermally activated delayed fluorescence (TADF) compounds bearing a tridentate 2,2′‐(pyridine‐2,6‐diyl)diphenolate (dppy) ligand has been successfully designed and synthesized. Upon varying the donor moieties from carbazole to 10H‐spiro[acridine‐9,9′‐fluorene] to 9,9‐dimethyl‐9,10‐dihydroacridine, these boron derivatives exhibit a wide range of emission colors spanning from blue to yellow with a large spectral shift of 2746 cm−1, with high PLQYs of up to 96 % in the doped thin film. Notably, vacuum‐deposited organic light‐emitting devices (OLEDs) made with these boron compounds demonstrate high performances with the best current efficiencies of 55.7 cd A−1, power efficiencies of 58.4 lm W−1 and external quantum efficiencies of 18.0 %. More importantly, long operational stabilities of the green‐emitting OLEDs based on 2 with half‐lifetimes of up to 12 733 hours at an initial luminance of 100 cd m−2 have been realized. This work represents for the first time the design and synthesis of tridentate dppy‐chelating four‐coordinate boron TADF compounds for long operational stabilities, suggesting great promises for the development of stable boron‐containing TADF emitters.

A series of luminescent cyclometalated rhodium­(III) complexes have been designed and prepared. The improved luminescence property is realized by the judicious choice of a strong σ-donor cyclometalating ligand with a lower-lying intraligand (IL) state that would raise the d–d excited state and introduction of a lower-lying emissive IL excited state. These complexes exhibit high thermal stability and considerable luminescence quantum yields as high as up to 0.65 in thin film, offering themselves as promising light-emitting materials in OLEDs. Respectable external quantum efficiencies of up to 12.2% and operational half-lifetimes of over 3000 h at 100 cd m–2 have been achieved. This work demonstrates a breakthrough as the first example of an efficient rhodium­(III) emitter for OLED application and opens up a new avenue for diversifying the development of OLED materials with rhodium metal being utilized as phosphors.