Highly symmetrical polyfluorinated porphyrazines

By cyclotetramerization of 2,3-bis[2-fluoro-5-(trifluoromethyl)benzylthio] maleonitrile in the presence of magnesium butanolate, magnesium porphyrazinate carrying eight (2-fluoro-5-(trifluoromethyl)benzylthio) functional groups on the periphery positions has been synthesized. Conversion of the magnesium porphyrazinate into the metal-free derivative was achieved by treatment with trifluoroacetic acid. Further reaction of this product with different metal (II) acetates have led to the metallo porphyrazines. Then, chloro-octakis [2-fluoro-5-(trifluoromethyl)benzylthio] porphyrazinato iron (III) (FePzCl) was prepared by the reaction of metal-free porphyrazine with iron (II) acetate and further treatment with HCl solution. The monomeric bisaxial complex FePz(py)2 as well as the bridged complex [FePz(pyz)]n were formed as stable complexes by reacting FePzCl with pyridine or pyrazine, respectively. These novel complexes were characterized by elemental analysis, together with FT-IR, 1H NMR, 13C NMR, 19F NMR, UV–vis and mass spectral data.