Water and alcohol-soluble octakis-metalloporphyrazines bearing sulfanyl polyetherol substituents: Synthesis, spectroscopy and electrochemistry

Water-soluble metalloporphyrazines (2, 3, and 4) bearing peripherally functionalized bis[thioethoxy(ethoxy)ethanol] moieties have been prepared from the corresponding [2H]-2,3,7,8,12,13,17,18-octakis{2-[2-2-hydroxyethoxy)ethoxy]-ethylthio}porphyrazine and appropriate metal salts [Zn(acac)2, CoCl2, MnCl2] in non-aqueous polar solvents such as, alcohol and THF. Multifunctional polyetherolsulfanyl peripheral sites, the exocyclic site of porphyrazines, serve as weak interacting ionophore in a number of metal ions, such as AgI and PdII. The reactivity of the peripheral groups of MPzs was tested by spectrophotometric titration by AgI and PdII. The titration resulted in the formation of intractable less soluble black and dark-blue polynuclear porphyrazine complexes. The new compounds have been characterized by elemental analysis, FTIR, 1H NMR, UV–vis and MS (MALDI-TOF). The voltammetric investigation of the complexes showed common ligand and metal-based redox processes.