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.