A new class of cationic iridium(III) complexes of the form [(C^N)2Ir(N^N)][PF6] is reported, where C^N = cyclometallating 2-phenylpyridinato, ppy, or 2-(2,4-difluorophenyl)-5′-methylpyridinato, dFMeppy, and N^N = guanidyl-pyridine, gpy, or pyrazine, gpz, as the ancillary ligand. A large blue-shift in the emission coupled with a 7-to-9 fold enhancement in photoluminescence quantum yield and microsecond emission lifetimes were observed for the complexes containing the partially saturated gpy ligand as compared to the benchmark complex [(ppy)2Ir(bpy)][PF6], C1, where bpy is 2,2′-bipyridine.