Synthesis and characterization of durene-capped porphyrins and the crystal structure of a hemin derivative

Sterically hindered porphyrins having a fully hydrophobic cavity have been prepared. The cavity is capped with a 2,3,5,6-tetramethylbenzene moiety containing at the 1,4-positions methylene —(CH2)n— chains (n = 4, 5, 7) bonded at trans pyrrole rings of a porphyrin that is alkylated with methyl or ethyl groups at the other β-pyrrolic positions. The iron(III) chloride derivative of the 4,4-durene-capped base has been obtained as single crystals, and subjected to X-ray structural analysis. The typical high spin, square pyramidal geometry of five-coordinate hemin chlorides is maintained; the porphyrin core is strongly distorted and there is no interaction between the phenyl group of the strap and the iron.