Ligand Controls the Activity of Light‐Driven Water Oxidation Catalyzed by Nickel(II) Porphyrin Complexes in Neutral Homogeneous Aqueous Solutions

Finding photostable, first‐row transition metal‐based molecular systems for photocatalytic water oxidation is a step towards sustainable solar fuel production. Herein, we discovered that nickel(II) hydrophilic porphyrins are molecular catalysts for photocatalytic water oxidation in neutral to acidic aqueous solutions using [Ru(bpy)(3)](2+) as photosensitizer and [S(2)O(8)](2−) as sacrificial electron acceptor. Electron‐poorer Ni‐porphyrins bearing 8 fluorine or 4 methylpyridinium substituents as electron‐poorer porphyrins afforded 6‐fold higher turnover frequencies (TOFs; ca. 0.65 min(−1)) than electron‐richer analogues. However, the electron‐poorest Ni‐porphyrin bearing 16 fluorine substituents was photocatalytically inactive under such conditions, because the potential at which catalytic O(2) evolution starts was too high (+1.23 V vs. NHE) to be driven by the photochemically generated [Ru(bpy)(3)](3+). Critically, these Ni‐porphyrin catalysts showed excellent stability in photocatalytic conditions, as a second photocatalytic run replenished with a new dose of photosensitizer, afforded only 1–3 % less O(2) than during the first photocatalytic run.