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A new cyclometalating ligand, featuring nitrile moieties to enhance the photophysical and consequently photocatalytic properties of bis-cyclometalated Ir(iii) complexes, was synthesized. Nitrile moieties were selected to replace expensive and environmentally problematic fluoride moieties commonly employed for synthetic tuning of chromophores. Two new chromophores bearing the new nitrile-decorated ligand were synthesized with strong electron-donating and electron-withdrawing ancillary ligands to probe extremes of the complexes’ tunability. These complexes possessed rich and drastically different electrochemical and photophysical properties. One chromophore possessed a particularly long lifetime of approximately 8 μs; it was also a remarkably efficient triplet emitter with a quantum yield of 63%. The complexes were finally assessed as photosensitizers of water reduction with Pt colloids, where both complexes produced hydrogen with optimized conditions reaching 2000 and 1400 turnovers. [ABSTRACT FROM AUTHOR]