Complexation and Crystallization of Anionic Phthalocyanine with Soluble and Cross-Linked Polycations

The complexation and crystallization of the tetrasodium salt of copper tetrasulfophthalocyanine (CuTSPc) with the solvated polycations poly((acryloyloxy)ethylpyridinium bromide) (PC2py) and poly((acryloyloxy)dodecylpyridinium bromide) (PC12py) and their gels were studied. CuTSPc binds to PC2py cooperatively and stoichiometrically, while it binds to PC12py in a cooperative but nonstoichiometric way. The wide-angle X-ray diffraction (WAXD) pattern of the CuTSPc−PC12py complex showed high crystallinity, in which the CuTSPc molecules formed hexagonal columns. On the other hand, diffraction peaks were weaker in the WAXD pattern of the CuTSPc−PC2py complex. The longer side chain of the polycations gives the bound CuTSPc molecules sufficient mobility and space to form better organized crystals. The complex of the CuTSPc-PC12py gel also crystallized despite the low mobility of the side chain since the main chain is restrained by cross-linkages.