The present contribution summarizes the most recent results on the synthesis and chemical physical characterization of the new classes of porphyrazine macrocycles having annulated five- and seven-membered heterocyclic rings, i.e. tetrakis(thiadizole)porphyrazine, TTDPzH 2, tetrakis(selenodiazole)porphyrazine, TSeDPzH 2, tetrakis-2,3-(5,7dipheny-6H-1,4-diazepino)porphyrazine, Ph 8 DzPzH 2, and a number of their metal derivatives, prepared by using, respectively, 3,4-dicyano-1,2,5-thiadiazole, 3,4-dicyano-1,2,5-selenodiazole, and 5,7-diphenyl-2,3-dicyano-6H-1,4-diazepine as monomeric precursors. The available information indicates that, owing to the presence of electron rich and soft atoms ( S , Se ) inserted in the proximity of the porphyrazine core, the TTDPz and TSeDPz macrocycles, closely resembling their phthalocyanine analogues in terms of structural and electronic features and physical behaviour (solubility, thermal stability, vaporizability, etc.), might be promising new materials for applicative properties. Particularly interesting is the operated peripheral ring opening of the TSeDPz macroxycle leading to the formation of octaaminoporphyrazine, followed by its conversion to a tetrakis(pyrazino)porphyrazine. The macrocycles containing the Ph 8 DzPz skeleton, due to the presence of the external non planar diphenyldiazepine units, appear to exhibit a distinct physical behaviour, which can be probably modulated by appropriate alternative substitutions in the 5, 6, and 7 positions of the diazepine rings.
Characterization of Sardinian Bentonite