Herein we report the synthesis of 4-aryl-1-benzyl-1H-1,2, 3-triazoles (ad), made via "Click chemistry" and their incorporation as cyclometallating ligands into new heteroleptic iridium(III) complexes containing diimine ((NN)-N-Lambda) ancillary ligands 2,2'-bipyridine (bpy) and 4,4'-di-tert-butyl-2,2'-bipyridine (dtBubpy). Depending on decoration, these complexes emit from the yellow to sky blue in acetonitrile (ACN) solution at room temperature (RT). Their emission energies are slightly blue-shifted and their photoluminescent quantum efficiencies are markedly higher (between 25 and 80%) than analogous ((CN)-N-Lambda)(2)Ir((NN)-N-Lambda)(+) type complexes, where (CN)-N-Lambda is a decorated 2-phenylpyridinato ligand. This increased brilliance is in part due to the presence of the benzyl groups, which act to sterically shield the iridium metal center. X-ray crystallographic analyses of two of the atl complexes corroborate this assertion. Their electrochemistry is reversible, thus making these complexes amenable for inclusion in light-emitting electrochemical cells (LEECs). A parallel computational investigation supports the experimental findings and demonstrates that for all complexes included in this study, the highest occupied molecular orbital (HOMO) is located on both the aryl fragment of the ad ligands and the iridium metal while the lowest unoccupied molecular orbital (LUMO) is located essentially exclusively on the ancillary ligand.