In this research, the electrochemical oxidation of meso-tetraphenylporphyrin (H₂TPP) has been studied in two solvents, benzonitrile and dichloromethane, with Bu₄NClO₄ as supporting electrolyte. Three oxidation waves are observed during the anodic sweep; the first two of nature quasi-reversible, and the third irreversible (Fig.1 a,b). The processes occurring at the first and second waves have been assigned to the formation of cation radical and dication, respectively¹. Cyclic voltammograms show that when the switching potential occurred after peak IIa, a reduction peak is observed around -0.17 V vs Fc⁺/Fc (IIIc); this peak, along with the third oxidation wave (IIIa), might be associated to the formation of isoporphyrin. Our hypothesis is that traces of water in the solvent can act as nucleophiles at the meso position of porphyrin dication, giving rise to the isoporphyrin species². Absorption bands at 445, 755, 794 and 883 nm observed during thin layer spectroelectrochemical UV-visible experiments (Fig.1 c,d,e) are also consistent with the formation of isoporphyrins following the formation of the dication^3,4. Long-term experiments such as controlled potential electrolysis show that isoporphyrins can also be formed from the cation radical, however this reaction seems to be too slow to affect the voltammograms. Exhaustive electrolysis at the potential of the first oxidation peak Ia, consumed about one-electron per molecule, and at the end of the electrolysis an anodic sweep revealed the disappearance of peak Ia; in a cathodic sweep, peak IIIc was observed. When the electrolyzed solution containing the isoporphyrin was reduced to the starting porphyrin at a potential slightly cathodic from of wave IIIc, the original anodic signals of H₂TPP were restored, showing the reversibility of the process. Similar results were obtained in both solvents. This demonstrates the existence of at least two reaction pathways, one for the formation of isoporphyrins from the radical cation H₂TPP^•+ at longer time scales, and other from H₂TPP⁺² at shorter times. This results contrast with previous studies that have shown that in benzonitrile the radical cation of the free-base porphyrins undergoes hydrogen atom abstractions leading to diprotonated species⁵, and with experiments using Bu₄NPF₆ in CH₂Cl₂ that do not lead to isoporphyrin species.

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