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.