New polyfluorinated porphyrazine complexes: synthesis, characterization, aggregation, and solubility

Abstract

By cyclotetramerization of 2,3-bis(2,3,5,6-tetrafluoro-4-methylbenzylthio)maleonitrile in the presence of magnesium butoxide, magnesium porphyrazinate (MgPz) carrying eight (2,3,5,6-tetrafluoro-4-methylbenzylthio) functional units on the periphery positions has been synthesized. Conversion of MgPz into the metal-free derivative was achieved upon addition of a strong acid such as trifluoroacetic acid. Further reaction of this product with different metal(II) acetates led to metallo porphyrazines (MPz). 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 complexes were characterized by elemental analysis, together with FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, UV–vis, and mass spectral data.

Keywords:

• 4-Methyl-2,3,5,6-tetrafluorobenzyl bromide
• pyrazine
• ¹⁹F NMR Spectroscopy
• oligomeric complex
• aggregation