Two new Mg-II porphyrazine macrocycles, the octakis(2-pyridyl)porphyrazinato-magnesium(II), [Py(8)PzMg-(H2O)], and the tetrakis-[6,7-di(2-pyridyl)quinoxalino]porphyrazinato-magnesium(II), [Py(8)QxPzMg(H2O)], were prepared by Mg-template macrocyclization processes, and their general physicochemical properties were examined. The previously reported porphyrazine analog, the tetrakis-2,3-[5,6-di(2-pyridyl)-pyrazino]porphyrazinato-magnesium(II), [Py(8)PyzPzMg(H2O)], has been also considered in the present work. The UV visible solution spectra in nonaqueous solvents of this triad of externally octapyridinated Mg-II complexes exhibit the usual profile observed for phthalocyanine and porphyrazine macrocycles, with intense absorptions in the Soret (300-450 nm) and Q band (600-800 nm) regions. It is observed that the Q band maximum sensibly shifts toward the red with peak values at 635 -> 658 -> 759 nm along the series [Py(8)PzMg(H2O)], [Py8PyzPzMg(H2O)], and [Py(8)QxPzMg(H2O)], as the extension of the macrocycle pi-system increases. TDDFT calculations of the electronic absorption spectra were performed for the related water-free model compounds [Py(8)PzMg], [Py(8)PyzPzMg], and [Py(8)QxPzMg] to provide an interpretation of the UV visible spectral changes occurring upon introduction of the pyrazine and quinoxaline rings at the periphery of the Pz macrocycle. To discriminate the electronic effects of the fused exocylic rings from those of the appended 2-pyridyl rings, the UV-visible spectra of [PzMg] and [PyzPzMg] were also theoretically investigated. The theoretical results prove to agree very well with the experimental data, providing an accurate description of the UV-visible spectra. The observed spectral changes are interpreted on the basis of the electronic structure changes occurring along the series.