Synthesis and characterization of O- and S-bridged perfluoroalkylated metal-free and zinc phthalocyanines

Abstract

The synthesis of tetra and octa perfluoroalkyl substituted zinc and metal free phthalocyanines (ZnPc and H 2 Pc) are reported. The compounds 1-5 have been prepared by nucleophilic substitution of 4-nitrophthalonitrile with 1H,1H,2H,2H-perfluorooctanethiol, 1H,1H,2H,2H-perfluorodecan-1-ol, 1H,1H-perfluorodecan-1-ol, 1H,1H-perfluorotetradecan-1-ol and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol, respectively. The compounds 6-8 have been prepared by the reaction of 1H,1H,2H,2H-perfluorodecan-1-ol, 1H, 1H-perfluorodecan-1-ol and 1H, 1H-perfluoro-3,6,9-trioxatridecan-1-ol with 4,5-dichlororphthalonitrile, respectively. The compound 9 with thia-bridge has been synthesized from 4,5-dichlororphthalonitrile. Zinc and metal free phthalocyanines were obtained from the corresponding phthalonitrile derivatives. All compounds were characterized by using mass, H-1, F-19 NMR, UV-vis and FT-IR as well as elemental analysis. Tetra substituted Zn(II) phthalocyanines are slightly soluble only in THF (Compound 4a and 7a are insoluble) but metal free phthalocyanines are not soluble. Octa substituted Zn(II) and metal free phthalocyanine are soluble in polar solvents such as THF and DMSO.