Synthesis and characterization of novel metal-free and metallo-porphyrazines with eight 3-thiopropylpentafluorobenzoate units

Metal-free and metallo-porphyrazines (M = 2H, Mg, Cu, Zn or Co) with eight polyfluorinated groups appended on the periphery through flexible alkylthio-bridges have been synthesized through esterification of octakis(hydroxypropylthio)porphyrazinato magnesium with 2,3,4,5,6-pentafluorobenzoic acid in the presence of dicyclohexylcarbodiimide (DCCI) and toluene-p-sulfonic acid. The symmetrically functionalized porphyrazines with eight ester units are soluble in common organic solvents, such as CHCl3, CH2Cl2, THF, acetone and toluene, and are insoluble in water and n-hexane. The newly synthesized compounds were characterized by FT-IR, UV–Vis, mass, 1H, 13C and 19F NMR, together with elemental analysis.

Graphical abstractMetal-free and metallo-porphyrazines carrying eight hydroxypropylsulfanyl units at the peripheral positions were synthesized from 2,3-bis(3-hydroxypropylthio)maleonitrile. The reactivity of the hydroxypropyl units was demonstrated by the esterification of porphyrazine derivatives with 2,3,4,5,6-pentafluorobenzoic acid in the presence of dicyclohexylcarbodiimide (DCCI) and toluene-p-sulfonic acid. The newly synthesized complexes were characterized by several spectroscopic methods.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Novel porphyrazine molecules with polyfluoro-substituents are synthesized. ► Solubility of complexes by esterification in common solvents is enhanced. ► In the aggregation work, no novel Q-band absorptions are observed. ► Enabled scientists to use as catalysts, soluble dyes, and optical recording agents.