Functional metal‐porphyrazine derivatives and their polymers, 1. Synthesis of metal‐[2,9or10(or 2,16or17)bis(3,4‐dicarboxybenzoyl)]phthalocyanine derivatives

The diimide of metal‐[2,9or10(or 2,16or17)bis(3,4‐dicarboxybenzoyl)]phthalocyanine(diPc) (where i = imide) 2 or 3 were prepared from 3,4,3′,4′‐benzophenonetetracarboxylic dianhydride (BTDA) (1), phthalic anhydride (PA), urea, and metal salts such as CuCl2, CoCl2, and FeCl3 etc. at 170°C. In the case of copper, the diPc monomer 2 or 3 and the dimer 4 or 5 could be synthesized. Those copper complexes are stable to all of the chemical procedures. However, the core metals of Fe(III), Co(II), Ni(II) and Zn(II)‐diPc were partially removed in the acid treatment. Metal phthalocyanine derivatives which have four carboxyl groups in the peripheral site, metal‐[2,9or10(2,16or17)bis(3,4‐dicarboxybenzoyl)] phthalocyanine(daPc) (a = acid) 6 or 7, were synthesized by hydrolysis of the metal‐diPc. The metal‐daPc are soluble in water, in aprotic solvents such as N,N′‐dimethylformamide, and also in sulfuric acid. The physicochemical properties of some metal‐daPc derivatives were investigated.