Synthesis and properties of novel polymeric metal-free and metallophthalocyanines containing peripherally long 1,2-bis[(3-oxapropyl)oxa]benzene derivatives

Abstract

New polymeric phthalocyanine moieties (M = 2H, Zn, Ni, Cu, and Co) were synthesized via polytetracyclomerization reaction of o-bis[3-(3,4-dicyanophenoxy)propyloxy]benzene (3), which can be obtained by the reaction of 4-nitrophthalonitrile with o-bis[(3-hydroxypropyl)oxy]benzene. Aggregation and disaggregation behavior of the polymeric phthalocyanine (5) was studied with some alkali and earth alkali metal cations. Measured intrinsic viscosities of the polymeric phthalocyanines exhibited a substantial decreasing tendency with dilution of the solution. Thermogravimetric analysis was performed under air by using DSC and DTG/TGA techniques and indicated that these polymers have good thermal stability. AC and DC electrical conductivities of the polymeric phthalocyanines were investigated in the frequency range 100 Hz--1 MHz within the temperature range 298--343 K. AC/DC conductivities of the samples were found to be between 10-5 and 10-7 S cm-1 at ambient temperature under argon atmosphere. The structures of new synthesized compounds were characterized by using microanalysis; various spectroscopic methods such as UV-Vis, FT-IR, 1H NMR, and 13C NMR spectroscopy; and MS spectra.