Directly-Fused Ni(II)Porphyrin Conjugated Polymers with Blocked meso-Positions: Impact on Electrocatalytic Properties

The oxidative coupling reaction of two Ni(II) porphyrins meso-substituted with three and four phenyl groups, Ni(II) 5,10,15-(triphenyl)porphyrin (NiPh₃P) and Ni(II) 5,10,15,20-(tetraphenyl)porphyrin (NiPh₄P) respectively, was investigated in a oxidative chemical vapor deposition (oCVD) process. Irrespective of the number of meso-substituents, high-resolution mass spectrometry evidences the formation of oligomeric species containing up to five porphyrin units. UV-Vis-NIR and XPS analyses of the oCVD films highlighted a strong dependence of the intermolecular coupling reaction with the substrate temperature. Specifically, higher substrate temperatures yield lowering of valence band maxima and reduction of the band gap. The formation of conjugated polymeric assemblies results in increased conductivities as compared to their sublimed counterparts. Yet, electrocatalytic measurements exhibit water oxidation onset overpotentials (308 mV for pNiPh₃P and 343 mV for pNiPh₄P) comparatively higher than the onset overpotential measured for the oCVD film from Ni(II) 5,15-(diphenyl)porphyrin (pNiPh₂P), i. e. 283 mV. Although DFT and comparative oCVD studies suggest the formation of directly fused porphyrins involving 'phenyl-mediated' and β-β linkages when reacting tetra-meso-substituted porphyrins, the present findings highlight that multiple direct fusion (β-β/meso-meso/β-β or meso-β/β-meso) is essential for Ni(II) porphyrin-based conjugated polymers to enable a dinuclear radical oxo-coupling operating mechanism for water oxidation at low overpotential and durable catalytic activity.