The synthesis and characterization of a shish kebab type oligomer with eight [3-thiopropyl 2-fluoro-5-(trifluoromethyl)phenylacetate] units

The functionality of hydroxypropylsulfanyl units of metal-free and metallo-porphyrazines, which are new compounds (M = 2H, Mg, Co, Cu or Zn), has been produced by esterification with a carboxylate group such as 2-fluoro-5-(trifluoromethyl)phenylacetic acid. The symmetrically functionalized porphyrazines, with eight ester units, are soluble in common organic solvents such as chloroform, dichloromethane, tetrahydrofuran, dimethylsulfoxide, acetone and toluene, and insoluble in water and n-hexane. Chloro-octakis[3-thiopropyl 2-fluoro-5-(trifluoromethyl)phenylacetate] porphyrazinato iron(III) (FePzCl) was prepared by the reaction of the metal-free porphyrazine and iron(II) acetate, followed by treatment with HCl solution. The monomeric bis-axial complex [FePz(py)2], as well as the bridged complex [FePz(pyz)]n, were formed as stable complexes by reacting FePzCl with pyridine and pyrazine, respectively. The novel compounds have been characterized by several spectroscopic techniques, such as FT-IR, UV–Vis, mass, 1H, 13C and 19F NMR, and elemental analysis.

Graphical abstractMetal-free and metallo-porphyrazines with eight 2-fluoro-5-(trifluoromethyl)phenylacetate units appended on the periphery through flexible thiopropyl-bridges have been synthesized through the esterification of octakis(hydroxypropylthio)porphyrazinato magnesium with 2-fluoro-5-(trifluoromethyl)phenylacetic acid in the presence of dicyclohexylcarbodiimide (DCCI) and toluene-p-sulfonic acid. Chloro-octakis[3-thiopropyl 2-fluoro-5-(trifluoromethyl)phenylacetate] porphyrazinato iron(III) (FePzCl) was then prepared by the reaction of the metal-free porphyrazine and iron(II) acetate, followed by further treatment with HCl solution. The monomeric bis-axial complex [FePz(py)2] as well as the bridged complex [FePz(pyz)]n were formed as stable complexes by reacting FePzCl with pyridine and pyrazine, respectively. The synthesized complexes have been characterized by several spectroscopic methods.Figure optionsDownload full-size imageDownload as PowerPoint slide