Over the past two decades, photocatalysis has become an invaluable synthetic tool as it permits the generation of reactive radical intermediates under relatively mild conditions that ultimately lead to the formation of products, some of which cannot be accessed under thermal activation conditions. Photocatalysis operates through the selective photoexcitation of a photocatalyst (PC) into its electronically excited state (PC*). Subsequently, the PC* relaxes rapidly via a combination of internal conversion and vibrational relaxation to its S1 excited state. The presence of a heavy metal atom in transition metal complex PCs mediates an ultra-rapid intersystem crossing to populate the triplet excited state, which for iridium complexes typically occurs on the picosecond time scale. Intermolecular photocatalysis occurs following diffusion of the PC* to interact with a substrate (S) to form an encounter complex, which typically occurs on the nanosecond time scale. The subsequent photochemistry predominantly proceeds by one of two mechanistic pathways: photoinduced energy transfer (PEnT) or photoinduced electron transfer (PET). PEnT typically occurs though either a Förster or Dexter energy transfer mechanism, while in a PET (aka photoredox) pathway, the PC* undergoes either oxidative (PC* is oxidized to PC +• , and S is reduced to S -• ) or reductive (PC* is reduced to PC -• , and S is oxidized to S +• ) quenching, depending on the direction of the single electron transfer (SET). To close the photocatalytic cycle requires that the oxidized or reduced PC undergoes a second SET event to regenerate its ground state. Organometallic Ir(III) and Ru(II) complexes are arguably still the most widely used class of PCs. In particular, Ir(III) PCs are either neutral homoleptic complexes of the type Ir(C^N)3 and almost always are used as their facial isomer, or are heteroleptic cationic complexes of the form [Ir(C^N)2(N^N)] + (C^N represents a cyclometalating ligand such as 2-phenylpyridinato and N^N represents a diimine type ligand like 2,2'-bipyridine). The appeal of these complexes lies in their readily tuneable redox potentials as a function of ligand electronics and that they possess absorption bands into the visible region, permitting selective photoexcitation. The efficacy and versatility of these Ir(III) PCs has been documented over the past twenty years across a wide range of different photocatalytic transformations. However, despite their popularity, the photocatalytic properties of the derivatives that are typically used are somewhat limited. In particular, the triplet energies (ET) of the most commonly used Ir PCs do not typically exceed 2.75 eV and their photoreducing strength does not exceed -2.1 V vs. SCE (Figure ). This limits their ability to activate more challenging substrates in both PEnT and PET reactions.