Magnesium porphyrazine having eight 5-hydroxypentylthio groups at the peripheral positions, was synthesized from 2,3-bis(5-hydroxypentylthio) maleonitrile. By the esterification reaction of octakis(5-hydroxypentylthio) porphyrazinato] Mg(II) with 3,4,5-trimethoxybenzoic acid in dicyclohexylcarbodiimide and toluene-p-sulfonic acid, esterified MgPz appending [5-thiopentyl 2-methoxy-4,6-bis(trifluoromethyl) benzoate] substituent was obtained. Further reaction of the metal-free porphyrazine with Co(II), Cu(II), Zn(II), and Fe(II) acetates have produced the metallo-porphyrazines. By reacting FePzCl with pyridine or pyrazine, the monomeric bis-axial and the oligomeric complexes were synthesized as the novel stable complexes, respectively. Their characterizations were performed by using elemental analysis, FT-IR, H-1-NMR, C-13-NMR, mass and UV-Vis spectral data. The aggregation investigations carried out in different concentrations indicate that 3,4,5-trimethoxybenzyloxy-substituted porphyrazine compounds do not have any aggregation behavior in different concentrations. Quantum chemical computations were also done to the structural and electronic properties of target compounds.