Switching Catalyst Selectivity via the Introduction of a Pendant Nitrophenyl Group

The conversion of abundant small molecules to value-added products serves as an attractive method to store renewable energy in chemical bonds. A family of macrocyclic cobalt aminopyridine complexes was previously reported to reduce CO₂ to CO with 98% faradaic efficiency through the formation of hydrogen-bonding networks and with the number of secondary amines affecting catalyst performance. One of these aminopyridine macrocycles, (NH)₁(NMe)₃-bridged calix[4]­pyridine (L⁵), was modified with a nitrophenyl group to form L^NO2 and metalated with a cobalt­(II) precursor to generate CoL^NO2, which would allow for probing the positioning and steric effects on catalysis. The addition of a nitrophenyl moiety to the ligand backbone results in a drastic shift in selectivity. Large current increases in the presence of added protons and CoL^NO2 are observed under both N₂ and CO₂. The current increases under N₂ are ∼30 times larger than the ones under CO₂, suggesting a change in the selectivity of CoL^NO2 to favor H₂ production versus CO₂ reduction. H₂ is determined to be the dominant reduction product by gas chromatography, reaching faradaic efficiencies up to 76% under N₂ with TFE and 71% under CO₂ with H₂O, in addition to small amounts of formate. X-ray photoelectron spectroscopy (XPS) reveals the presence of a cobalt-containing heterogeneous deposit on the working electrode surface, indicating the addition of the nitrophenyl group reduces the electrochemical stability of the catalyst. These observed catalytic behaviors are demonstrably different relative to the tetra-NH bridged macrocycle, which shows 98% faradaic efficiency for CO₂-to-CO conversion with TFE, highlighting the importance of pendant hydrogen bond donors and electrochemically robust functional groups for selective CO₂ conversion.