Second‐Sphere Biomimetic Multipoint Hydrogen‐Bonding Patterns to Boost CO₂ Reduction of Iron Porphyrins

Inspired by nature's orchestra of chemical subtleties to activate and reduce CO₂ , we have developed a family of iron porphyrin derivatives in to which we have introduced urea groups functioning as multipoint hydrogen-bonding pillars on the periphery of the porphyrinic ring. This structure closely resembles the hydrogen-bond stabilization scheme of the carbon dioxide (CO₂ ) adduct in the carbon monoxide dehydrogenase (CODH). We found that such changes to the second coordination sphere significantly lowered the overpotential for CO₂ reduction in this family of molecular catalysts and importantly increased the CO₂ binding rate while maintaining high turnover frequency (TOF) and selectivity. Entrapped water molecules within the molecular clefts were found to be the source of protons for the CO₂ reduction.