2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetraarylporphyrins and Their Zinc Complexes:  First Spectroscopic, Electrochemical, and Structural Characterization of a Perfluorinated Tetraarylmetalloporphyrin

We report a convenient and general synthesis of β-octafluoroporphyrins bearing meso-tetraaryl substituents, including the first synthesis and full characterization of a perfluorinated tetraarylporphyrin, perfluoro-5,10,15,20-tetraphenylporphyrin, 2. The structural, spectroscopic, and electrochemical data indicate that β-octafluoro-meso-tetraarylporphyrins are a new class of planar, electron-deficient ligands. Particularly impressive is the 0.5 V window over which the formal oxidation potential can be tuned using only aryl substituents. The invariance of the ligand structure with increasingly positive formal oxidation potential is a key advance; electronic effects have been severed from the nonplanar conformations exhibited by all other highly electron-deficient porphyrins.