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.

Graphical abstract4-{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]ethoxy}, 4-chloro-5-{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy] ethoxy}, and 4,5-bis{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]ethoxy} substituted metal free (H2Pc) and metallophthalocyanines (NiPc, ZnPc, CoPc) were synthesized for the first time in this study. These complexes were characterized by mass, FT-IR and UV–vis spectroscopic techniques as well as elemental analysis.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► For the first time Zn2+, Ni2+, Co2+, 2H Pcs with fluoroethers were synthesized. ► Compounds were characterized by elemental analysis, IR, 1H, and 19F NMR, UV–vis, MS. ► Fluorine atoms increase the solubility in polar solvents such as acetone and THF. ► Aggregation properties in different solvents, at different concentrations are shown. ► Tetra and octa fluoroxy substitution is an efficient way to diminish aggregation.