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A series of phenanthroline-based ligands have been synthesised and their influence as bidentate nitrogen ligands in heteroleptic [Cu(P^P)(N^N)]+ photosensitisers in light-driven water reduction has been studied. In this noble-metal-free Cu-Fe-based photocatalytic water reduction system, the structural effects of the nitrogen ligands have been explored, including the steric and electronic effects of substituents at the 2,9- and 4,7-positions of phenanthroline. Ligands were prepared that led to increased hydrogen generation, with turnover numbers (TONCu) of up to 1388 being observed. All the new complexes were electrochemically and photophysically characterised. We demonstrate for the first time that the presence of fluorine in nitrogen ligands increases the efficacy of copper complexes in photocatalytic hydrogen production. [ABSTRACT FROM AUTHOR]

In situ generated iron-based Knölker complexes were found to be efficient catalysts in a fully non-noble metal Cu-Fe photocatalytic water reduction system. These mononuclear iron catalysts were able to generate hydrogen up to 15 times faster than previously reported [Fe3(CO)12]. A reductive quenching mechanism was shown to operate by fluorescence experiments. [ABSTRACT FROM AUTHOR]