Procedures for the preparation of metal-free phthalocyanine network polymers from oxygen-, sulfur-, and selenium-bridged bis(phthalonitrile) monomers were investigated on the basis of phthalocyanine model compounds derived from phenoxy-, (phenylthio)-, and (phenylseleno) phthalonitrile compounds. The oxygen-and sulfur-substituted phthalonitrile compounds could be converted in high yield to the corresponding metal-free phthalocyanine compounds by reaction with tetrahydropyridine, hydroquinone, or 4,4'-biphenol. With an optimum quantity of coreactant, the phthalocyanine yield ranged from near-quantitative to 65% to no conversion for the respective oxygen, sulfur, and selenium phthalonitriles. A side reaction to a triazine structure was also investigated. The model phthalocyanine compounds were characterized by IR, electronic, NMR, and X-ray diffraction spectroscopies and TGA, from which an analysis of the corresponding phthalocyanine network polymers was made. Spectroscopic analysis and sulfuric acid insolubility indicated a significantly higher phthalocyanine content in the oxygen-bridged network polymer. Both phthalocyanine model compounds and network polymers had very high electrical resistivities, and the polymers were not dopable with iodine.

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