-Tris(heteroleptic) Red Phosphorescent Iridium(III) Complexes Bearing a Dianionic ,,','-Tetradentate Ligand.

1-Phenyl-3-(1-phenyl-1-(pyridin-2-yl)ethyl)isoquinoline (HMeL) has been prepared by Pd(-XantPhos)-catalyzed "" to synthesize new phosphorescent red iridium(III) emitters (601-732 nm), including the carbonyl derivative Ir(κ--,'--,'-MeL)Cl(CO) and the acetylacetonate compound Ir(κ--,'--,'-MeL)(acac). The tetradentate 6e-donor ligand (6tt') of these complexes is formed by two different bidentate units, namely, an orthometalated 2-phenylisoquinoline and an orthometalated 2-benzylpyridine. The link between the bidentate units reduces the number of possible stereoisomers of the structures [6tt' + 3b] (3b = bidentate 3e-donor ligand), with respect to a [3b + 3b' + 3b″] emitter containing three free bidentate units, and it permits a noticeable stereocontrol. Thus, the isomers -Ir(κ--,'--,'-MeL){κ-,-(CH-py)}, -Ir(κ--,'--,'-MeL){κ-,-(CHR-py)}, and -Ir(κ--,'--,'-MeL){κ-,-(CHR-py)} (R = H, Me) have also been selectively obtained. The new emitters display short lifetimes (0.7-4.6 μs) and quantum yields in a doped poly(methyl methacrylate) film at 5 wt % and 2-methyltetrahydrofuran at room temperature between 0.08 and 0.58. The acetylacetonate complex Ir(κ--,'--,'-MeL)(acac) has been used as a dopant for a red PhOLED device with an electroluminescence λ of 672 nm and an external quantum efficiency of 3.4% at 10 mA/cm.