were first reported as emitters almost two decades ago. Despite emitting in the deep-blue (lPL = 410 nm in dichloromethane, DCM), these complexes have low photoluminescence quantum yields (FPL = 2-5% in 2-methyltetrahydrofuran, 2-MeTHF), making them unattractive as emitters for OLEDs. The replacement of the pyridyl moiety of Ir(C^N)3 complexes like fac-Ir(ppy)3 with a strong-field C^C' ligand results in complexes with a destabilized LUMO that is evidenced by significantly cathodically shifted reduction potentials, and higher ET. An assessment of the optoelectronic properties of fac-and mer-Ir(pmi)3 illustrates their promise as photocatalysts. In MeCN, they have very negative E*ox of -2.67 and -2.72 V vs. SCE, and high ET of 3.30 and 3.28 eV, respectively for both. Our study reveals that both PCs consistently outperformed the strongly photoreducing archetypal photocatalyst fac-Ir(ppy)3 across a range of challenging energy transfer, oxidative quenching and copper dual metallaphotoredox catalysis transformations.