Narrow Results

We have synthesized a series of tetrakis(arylvinylene)phthalocyanines from the corresponding phthalonitriles. Substitution of the para-fluorine in the pentafluorphenyl ring with an alkoxy group from the solvent occurs during the synthesis. This substitution can be suppressed by the addition of zinc chloride or tin chloride to the reaction mixture. According to ¹H and ¹⁹F NMR data, the cis- or trans-conformations of the starting materials are retained during condensation; thus the phthalocyanines formed are in all-cis or all-trans form. Cis-trans photoisomerization occurs easily for phthalonitriles, while phthalocyanines retain their conformations under UV beam.

The synthesis of tetra and octa perfluoroalkyl substituted zinc and metal free phthalocyanines (ZnPc and H₂Pc) 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, ¹H, ¹⁹F 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.