Novel phthalocyanine polymers with very flexible pentathiatetraethylene units

A series of polymeric metal-free and metallophthalocyanine (M = 2H, Ni, Co, Fe, Pb, Cu and Zn) polymers were prepared by polymeric tetramerization reaction of bisphthalonitrile monomer with proper materials. The Co–phthalocyanine polymer was prepared by two different methods. The metal-free (3) and the Co-containing phthalocyanine polymer (5) were chemically doped with iodine (I2) and nitrosyl tetrafluoroborate (NOBF4), respectively. The electrical conductivities of the polymeric phthalocyanines measured as gold sandwiches were found to be 10−8–10−4 S cm−1 in vacuum and in argon. The electrical conductivities of I2-doped metal-free phthalocyanine (3a) and NOBF4-doped Co–phthalocyanine (5a) polymers were found to be approximately 110 and 89 times higher than those of undoped versions, respectively. The extraction ability of 3 was also evaluated in tetrahydrofuran using several transition metal picrates such as Ag+, Hg2+, Pb2+, Cd2+, Cu2+ and Zn2+. The extraction affinity of 3 for Ag+ was found to be highest in the heterogeneous phase extraction experiments. The aggregation and disaggregation properties of 3 were investigated with silver(I), mercury(II) and methanol as solvent. All the novel compounds were characterized by using elemental analysis, UV–vis, FT-IR, NMR and MS spectral data and DTA/TG.