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.

The new readily soluble metallo-porphyrazines with up to 32 fluorine-containing substituents on the periphery were reported and also the effects of the substituents on the spectroscopic properties of the porphyrazine complexes in different solvents were reported. However, iron porphyrazine derivatives with eight 2-fluoro-5-(trifluoromethyl)benzylthio substituents appending to the periphery positions were synthesized. Chloro {octakis [2-fluoro-5-(trifluoromethyl)benzylthio] porphyrazinato} iron (III) 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. By using different spectroscopic methods, novel compounds have been characterized.Figure optionsDownload as PowerPoint slideHighlights
► Novel soluble polyfluorinated porphyrazines are synthesized.
► Solubility of metallo porphyrazines in common solvents is enhanced.
► The synthesis of monomeric bisaxial complex was realized.
► The shish kebab type olygomer was synthesized with bidentate ligands.