Abstract
Directly fused nickel(ii) porphyrins are successfully investigated as heterogeneous single-site catalysts for the oxygen evolution reaction (OER). Conjugated polymer thin films from Ni(ii) 5,15-(di-4-methoxycarbonylphenyl)porphyrin (pNiDCOOMePP) and Ni(ii) 5,15-diphenylporphyrin (pNiDPP) showed an OER onset overpotential of 270 mV, and current densities of 1.6 mA cm-2 and 1.2 mA cm-2 at 1.6 V vs. RHE, respectively, representing almost a hundred times higher activity than those of monomeric thin films. The fused porphyrin thin films are more kinetically and thermodynamically active than their non-polymerized counterparts mainly due to the formation of conjugated structures enabling a dinuclear radical oxo-coupling (ROC) mechanism at low overpotential. More importantly, we have deciphered the role of the porphyrin substituent in the conformation and performance of porphyrin conjugated polymers as (1) to control the extension of the conjugated system during the oCVD reaction, allowing the retention of the valence band deep enough to provide a high thermodynamic water oxidation potential, (2) to provide a flexible molecular geometry to facilitate O2 formation from the interaction between the Ni-O sites and to weaken the π-bond of the *Ni-O sites for enhanced radical character, and (3) to optimize the water interaction with the central metal cation of the porphyrin for superior electrocatalytic properties. These findings open the scope for molecular engineering and further integration of directly fused porphyrin-based conjugated polymers as efficient heterogeneous catalysts.