Synthesis and Characterization of Crown‐Ether‐Containing Phthalocyanines with Group‐IV‐A Elements

Group‐IV‐A phthalocyanines with four crown ether substituents have been prepared from 4′,5′‐dicyanobenzo(15‐crown‐5), 4′,5′‐diiminoisoindolino(15‐crown‐5), or metal‐free phthalocyanine and the corresponding metal salts. The axial ligands of dichloro[tetra(15‐crown‐5)phthalocyaninato]silicon or ‐tin have been converted into dihydroxy derivatives by hydrolysis in aqueous Et3N. The catalytic effect of H2O‐free CaC12 in quinoline is used for the polycondensation of dihydroxysilicon‐phthalocyanine to cofacially arrayed polymers. The thermal stability of group‐IV‐A‐metal phthalocyanines is confirmed by the higher initial decomposition points (290–440°) compared to those of the corresponding transition‐metal phthalocyanines.