One‐Pot Synthesis of Contracted and Expanded Porphyrins with meso‐CF3 Groups

Corrole and sapphyrin with the smallest meso‐substituents reported so far were prepared in a one‐pot synthesis that relies on a non‐aldehydic precursor for introducing CF₃ groups. The substantial amounts of products obtained by this facile pathway allowed for the full characterization of 5,10,15‐tris(trifluoromethyl)corrole, the access to a variety of stable chelates thereof and investigations that disclose the unique structural and chemical properties induced by the CF₃ substituents. The novel 5,10,15,20‐tetra(trifluoromethyl)sapphyrin undergoes only single protonation, which according to its crystal structure is stabilized by favorable non‐bonding F/H interaction between the meso‐CF₃ and the inverted pyrrolic NH.