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)

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AbstractMetal‐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.