Amethyrin-type expanded porphyrins that display anti-aromatic character upon protonation

The use of protonation to switch nonaromatic expanded porphyrins to their corresponding anti-aromatic forms has not been widely explored. Here, we show that free-base pyriamethyrin and dipyriamethyrin display nonaromatic character, as inferred from NMR spectroscopic analyses, their optical properties, and theoretical calculations. Addition of two protons extends the π - conjugation of these amethyrin analogues and yields formally anti-aromatic systems.