Oxidative Cyclodehydrogenation Reactions with Tetraarylporphyrins

Abstract

The extension of the aromatic π‐system of porphyrins is a powerful method to alter their optoelectronic properties. Herein, aryl substituents were fused to porphyrin cores by Scholl oxidation reactions that selectively produced mono‐ and doubly‐fused porphyrins in yields of up to 69 %. Several different aryl substituents attached to the porphyrin were investigated with respect to their reactivity under Scholl conditions. The fused products were fully characterized, i.e., by UV/Vis absorption spectroscopy, which showed drastic changes in the electronic features. Insight into the solid‐state behavior was obtained by X‐ray crystallography. Our approach represents a novel option for the late‐stage functionalization of porphyrin‐based compounds.