The new octacations [(2-Mepy)(8)PzM](8+) [M = Mg-II(H2O), Zn-II], isolated as iodide salts, were obtained from the corresponding neutral complexes [Py(8)PzM] (Py = 2-pyridyl; Pz = porphyrazinato dianion) upon quaternization with CH3I of the N atoms of the 2-pyridyl rings under mild experimental conditions. The absorption spectra registered in organic solvents as well as in water (H2O) confirm the presence of the complexes in their monomeric form in all cases. The two octacations behave as photosensitizers in a H2O/sodium dodecyl sulfate solution for the production of singlet oxygen, O-1(2), and exhibit quantum yield values (Phi(Delta)) 2.2-2.5 higher than those measured for the standard PcAlSmix, a promising feature of interest for photodynamic therapy. The interaction of the Zn-II octacation [(2-Mepy)(8)PzZn](8+) with different types of DNA has been studied by means of optical spectroscopic techniques, clearly suggesting that binding of the charged macrocycle to the DNA effectively takes place. In order to assess the effect of the aromatic ring size, the same binding study was performed for the octapyridinated zinc(II) tetraquinoxalinoporphyrazine complex having a much more expanded macrocyclic framework and compared with the behavior of the parent octapyridinated zinc(II) tetrapyrazinoporphyrazine complex having an intermediate macrocycle. The achieved information confirms the relationship between the binding of the charged macrocycle to the DNA and the dimension of the porphyrazine macrocycle.