Synthesis and characterization of novel fluoroether-substituted phthalocyanines

The synthesis of 1H,1H-nonafluoro-3,6-dioxaheptan-1-ol with 4-nitrophthalonitrile and 4,5-dichlorophthalonitrile in the presence of K2CO3 leads to the formation of 4-{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]ethoxy}phthalonitrile (1), 4-chloro-5-{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy] ethoxy}-phthalonitrile (2), and 4,5-bis{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]ethoxy}phthalonitrile (3), respectively. Metal free phthalocyanines were synthesized by tetramerization of the phthalonitriles in 2-(dimethylamino)ethanol while metallophthalocyanines were prepared in the presence of zinc, cobalt or nickel salts. The new compounds were characterized by elemental analysis, IR, 1H, and 19F NMR and UV–Vis spectroscopy as well as mass spectrometry. The fluoroether substituted Pcs are best soluble in polar solvents such as acetone and THF.