In this work, we report a new class of blue-emitting cyclometalated iridium complexes supported by acyclic diaminocarbene (ADC) ancillary ligands. These neutral, tris-chelated complexes are not obtainable via traditional synthesis routes and instead are generated through metal-mediated nucleophilic addition to a metal-bound isocyanide, which is followed by orthometalation of the ADC under mild conditions. Importantly, four of the variants exhibit efficient phosphorescence when immobilized in PMMA matrix, achieving quantum yields of 79% for blue emitters with a 2-(2,4-difluorophenyl)pyridine (F(2)ppy) C<^>N ligand and 30-37% for orange emitters with a 2-phenylbenzothiazole (bt) C<^>N ligand. Electrochemical studies demonstrate significantly higher-lying HOMO levels in the ADC complexes relative to the NHC analogues, a phenomenon that results in enhanced charge-transfer character in the excited states of the ADC complexes. This study demonstrates that ADC ancillary ligands not only give rise to new structures for Ir(III)-based phosphorescent emitters but also are promising targets for use in light-emitting devices and other thin-film optical applications.