The way to prepare molecular emitters [St + 4t'] of iridium(III) with a St ligand derived from the abstraction of the hydrogen atom at position 2 of the aryl group of 1,3-di(2-pyridyl)benzene (dpybH) is shown. In addition, the photophysical properties of the new emitters are compared with those of their counterparts resulting from the deprotonation of 1,3-di(2-pyridy1)-4,6-dimethylbenzene (dpyMebH), at the same position, which are also synthesized. Treatment of 0.5 equiv of the dimer [Ir(mu-Cl)(eta(2)-COE)(2)](2) (COE = cyclooctene) with 1.0 equiv of Hg(dpyb)CI leads to the iridium(III) derivative IrCl2{kappa(3)-N,C,N-(dpyb)}(eta(2)-COE) (3), which reacts with 2-(1H-imidazol-2-yl)-6-phenylpyridine (HNImpyC(6)H(5)) and 2-(1H-benzimidazol-2-y1)-6-phenylpyridine (HNBzimpyC(6)H(5)) in the presence of Na2CO3 to give Ir{kappa(3)-C,N,N-(NImpyC(6)H(4))}{kappa(3)-N,C,N-(dpyb)} (4) and Ir{kappa(3)-C,N,N-(NBzimpyC(6)H(4) )}{k(3)-N,C,N-(dpyb)} (5), respectively. Similar reactions of the Williams's dimer [IrCl(mu-Cl){kappa(3)-N,C,N-(dpyMeb)}](2) with HNImpyC(6)H(5) and HNBzimpyC(6)H(5) in the presence of Na2CO3 afford the dimethylated counterparts IrCl(mu-C,N,N-(NImpyC(6)H(4))}{kappa(3)-N,C,N-(dpyMeb)} (6) and Ir{kappa(3) -C,N,N4NBzimpyC(6)H(4))}{kappa N3-,C,N-(dpyMeb)} (7), whereas 2-(6-phenylpyridine-2-yI)-1H-indole (HIndpyC 6 F1 5 ) initially gives IrH{kappa(3)-N,N-(IndpyC(6)H(5))}{kappa(3)-N,C,N-(dpyMeb)} (8) and subsequently Ir{kappa(3)-C,N,N-(IndpyC(6)H(4))}{kappa(3)-N,C,N-(dpyMeb)} (9). Complexes 4-7 are phosphor- escent green emitters (lambda(em) 490-550 nm), whereas 9 is greenish yellow emissive (lambda(em )547-624 nm). They display lifetimes in the range 0.5-9.7 mu s and quantum yields in both doped poly(methyl)methacrylate films and in 2-methyltetrahydrofuran at room temperature depending upon the ligands: 0.5-0.7 for 6 and 7, about 0.4 for 4 and 5, and 0.3-0.2 for 9.