Functional metal-porphyrazine derivatives and their polymers, 7. Synthesis and properties of metal-2,9,16,23-tetracarboxyphthalocyanine covalently bound to poly(2- or 4-vinylpyridine-co-styrene)†

Metal-2,9,16,23-tetracarboxyphthalocyanines(Mt-taPc's) [Mt = Fe(III), Co(II), Ni(II), Cu(II)] covalently bound to poly(2- or 4-vinylpyridine-co-styrene) were synthesized by Friedel-Crafts reaction of the styrene units of the copolymers with Mt-taPc tetraacid chloride. The copolymers contain about 0,3 to 14,6 mol-% Mt-Pc rings and are soluble in methanol, ethanol, and N,N-dimethylformamide. The coordination spheres around the Mt-Pc rings were characterized by electronic as well as ESR spectra and by viscosity measurements. The dimerization of Mt-taPc in the copolymers is sterically hindered by the polymer chain. The copolymer supported Fe(III)- or Co(II)-taPc's are of the five coordinate high spin type in DMF solution. One coordination site at axial position of the Mt-Pc ring may be occupied by an N atom of a pyridine group. The electronic structures of the metal atoms may be useful in catalytic reactions.