β‑Decamethoxysapphyrin and Its <i>N</i>‑Benzyl Analogue

The synthesis of a highly electron-rich decamethoxysapphyrin and its 27-N-benzyl analogue is reported for the first time. The effects of β-methoxy and 27-N-benzyl substitution on structure, anion binding, absorption, and electrochemical properties were explored in detail. Upon 27-N-benzyl substitution, counteranion-induced structural deformation arises in the diprotonated state, which could be clearly noticed both in solution 1H NMR study and solid-state structural analysis. This type of anion-induced structural deformation is noted for the first time in β-substituted sapphyrins. Further, the free base sapphyrins generate singlet oxygen with moderate efficiency (∼42%); hence, they may act as good photosensitizers.