Abstract

AbstractThe two‐electron reduction of a diprotonated dodecaphenylporphyrin derivative by Na2S2O4 gave a corresponding isophlorin (Iph) selectively. Formation of Iph was confirmed by spectroscopic measurements and the isolation of tetramethylated Iph. Further reduction of Iph proceeded to form an unprecedented four‐electron‐reduced porphyrin (IphH2), which was fully characterized by spectroscopic and X‐ray crystallographic analysis. IphH2, with a unique conformation, could be oxidized to reproduce the starting porphyrin, resulting in a proton‐coupled four‐electron reversible redox system.

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