Enrichment of solubility by esterification: Metal-free and metallo-porphyrazines with polyfluorinated units

Metal-free and metallo-porphyrazines (M = 2H, Mg, Cu, Zn or Co) 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 3,5-bis(trifluoromethyl)benzoic acid in the presence of dicyclohexylcarbodiimide and toluene-p-sulfonic acid. The symmetrical porphyrazine derivatives with eight ester units were soluble in common organic solvents such as chloroform, dichloromethane, THF, acetone, and toluene and insoluble in water and n-hexane. The complexes were characterized by several spectroscopic methods.