Synthesis and Investigation of Chalcogen Atom Substituted Dinitriles and Porphyrazines

A series of chalcogen atom substituted porphyrazines have been assembled and characterized. Oxygen and sulfur chalcogen atoms have been substituted for peripheral methylene groups. Heteroatom-enriched, seven-membered ring dinitriles (1–3) were synthesized and characterized by IR, MS, UV-vis, 1H NMR, elemental analysis, and X-ray analysis to examine the ring conformations. They were template cyclized in the presence of MgII to form the MgII containing porphyrazine macrocycles. The MgII and metal-free macrocycles (4–9) were synthesized for all peripherally substituted porphyrazines. The unchalcogen-substituted NiII, CuII, and ZnII containing porphyrazine derivatives (10–12) were also synthesized because of the higher solubility of the metal-free porphyrazine 7. The macrocycles were characterized and studied using such techniques as UV-vis, IR, elemental analysis, cyclic voltammetry, and electrical conductivity measurements.