Post-synthetic modification of hangman porphyrins synthesized on the gram scale.

We report a multi-gram scale synthesis of methyl 6-formyl-4-dibenzofurancarboxylate and its subsequent use in the gram scale synthesis of a dibenzofuran-functionalized hangman porphyrin containing a pendant carboxylic acid (HPD-CO2H). HPD-CO2H can be isolated as a free carboxylic acid in high purity with minimal purification. Post-synthetic modification of HPD-CO2H allows for the introduction of any desired pendant group in good yields, resulting in a practical amount of hangman porphyrin ligand with an easily customizable second coordination sphere. The cobalt complexes of these hangman porphyrins are shown to be active proton reduction electrocatalysts.