Heteropentanuclear porphyrazines having the formula [(PtCl2)(4)LM] where L = tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato dianion and M = Zn-II, Mg-11(H2O), Pd-II, Cu-II or Co-II were characterized by elemental analyses, IR-UV- visible spectroscopy and electrochemistry and the data compared to new and previously published results for the corresponding homopentanuclear compound [(PtCl2)(4)LPt]. This latter species has four external N2(py)PtCl2 coordination sites which closely resemble cis-platin, (NH3)(2)PtCl2, the potent chemotherapeutic anticancer drug, and is able to act as a photosensitizer for the generation of O-1(2), the cytotoxic agent in photodynamic therapy (PDT). UV-visible spectra and half wave potentials for reduction of [(PtCl2)(4)LM], [(PtCl2)(4)LPt], the parallel series of mononuclear [LM] compounds and the pentanuclear [(PdCl2)(4)LM] compounds were examined in the nonaqueous solvents dimethyl sulfoxide, pyridine, and dimethylformamide. The complete set of available data indicate that external coordination of the PtCl2 and PdCl2 units significantly increases the level of the electron-deficiency of the entire molecular framework despite the fact that these groups are far away from the central porphyrazine pi-ring system and have coordination sites nearly orthogonal to the plane of the macrocycle. The pentanuclear species [(M'Cl-2)(4)LM] (M' = pt(II), Pd-II) undergo multiple one-electron transfers and exhibit an easier reducibility as compared to related electrode reactions of the parent compounds [LM] having the same central metal. Aggregation phenomena and reducibility of the porphyrazines to their monoanionic form (prevalently in DMF) are observed for some of the examined compounds and were analyzed and accurately taken into account. Quantum yields of O-1(2) (Phi Delta), of interest in PDT, were measured for [(PtCl2)(4)LM] with M = Zn-II, Mg-II(H2O), or Pd-II and the related macrocycles [(PdCl2)(4)LM] and [LM] in dimethylformamide (DMF) and/or DMF preacidified with HCI (DMF/HCl, [HCl]: 1-2 x 10(-4) M). Excellent Phi(Delta) values (0.5-0.6) which qualify the compounds as potent photosensitizers in PDT were obtained for the pentanuclear species having Zn-II or Pd-II as central metal ions. The [(PtCl2)(4)LZn] and [(PtCl2)(4)LPd] complexes are of special interest as potential bimodal anticancer agents because of the incorporated four cis-platin-like functionalities.