Synthesis and characterization of new polymeric phthalocyanines substituted with diaza-18-crown-6 macrocycles through ethyleneoxy bridges

A tetranitrile monomer was synthesized by nucleophilic aromatic substitution of N,N′-bis(2-hydroxyethyl)-4,13-diaza-18-crown-6 onto 4-nitrophthalonitrile. A series of polymeric metal-free and metallophthalocyanine (M = 2H, Zn, Cu, Co and Ni) polymers was prepared by polymeric tetramerization reaction of the tetranitrile monomer with proper materials. The electrical conductivities of the polymeric phthalocyanines measured as gold sandwiches were found to be ∼10−9–10−4 S cm−1 in a vacuum and in argon. The extraction ability of the metal-free polymeric phthalocyanine was evaluated in tetrahydrofuran using several alkali metal picrates such as Li+, Na+, K+ and Cs+. The extraction affinity of the metal-free polymeric phthalocyanine for K+ was found to be highest in the heterogeneous solid–liquid phase extraction experiments. The disaggregation property of the metal-free polymeric phthalocyanine was investigated with sodium, potassium and ammonium ions and methanol. All the novel compounds were characterized by using elemental analysis, UV–Vis, FT-IR, NMR and MS spectral data and DTA/TG.

Metal-free and metallophthalocyanine polymers containing ethyleneoxy diaza-18-crown-6 units were synthesized from a tetranitrile monomer and the appropriate starting materials. Besides, their cation-binding abilities, disaggregation property, viscosities, electrical conductivities and thermal properties were evaluated. The novel compounds have been characterized by physical and spectroscopic techniques.Figure optionsDownload as PowerPoint slide