Synthesis of polyphthalocyanines by an oxidoreduction reaction initiated by the benzhydrol functional group. I. Model study

A novel route for the thermal conversion of bis(phthalonitrile)monomers into metal‐free phthalocyanine network polymers was investigated on the basis of a model study on the tetramerization reaction of 4‐benzoylphthalonitrile and benzhydrol derivatives into metal‐free phthalocyanine compounds. This procedure of conversion of phthalonitrile derivatives involved an oxidoreduction reaction initiated by the alcohol functional group of benzhydrol coreactant. The influence of molar ratio of phthalonitrile and benzhydrol functional groups, chemical environment of the benzhydrol reducing group has been studied by microcalorimetry and electronic spectroscopy. It was observed that the theoretical 4 : 1 phthalonitrile: benzhydrol molar ratio is respected and the reductive capacity of the benzhydrol group is increased by the electron withdrawing effect of its substituants.