Bioinspired motifs in proton and CO₂ reduction with 3d-metal polypyridine complexes

The synthesis of active and efficient catalysts for solar fuel generation is nowadays of high relevance for the scientific community, but at the same time poses great challenges. Critical requirements are mainly associated with the kinetic barriers due to the multi-proton and multi-electron nature of the hydrogen evolution reaction (HER) and the CO₂ reduction reaction (CO₂RR) as well as to selectivity issues. In this regard, natural enzymes can be a source of inspiration for the design of effective and selective catalysts to target such fundamental reactions. In this Feature Article we review some recent works on molecular catalysts for both the HER and the CO₂RR performed in our labs and other research teams which mainly address (i) the role of redox non-innocent ligands, to lower the overpotential for catalysis and control the selectivity, and (ii) the role of internal relays, to assist formation of catalytic intermediates via intramolecular routes. The selected exemplars have been chosen to emphasize that, although the molecular structures and the synthetic motifs are different from those of the active sites of natural enzymes, many affinities in terms of catalytic mechanism and functionality are instead present, which account for the observed remarkable performances under operative conditions. The data discussed herein thus demonstrate the great potential and the privileged role of molecular catalysts towards the design and construction of hybrid photochemical systems for solar energy conversion into fuels.