Tetra-2,3-pyrazinoporphyrazines with Peripherally Appended Pyridine Rings. 20. Mono- and Pentanuclear AlIII and GaIII Complexes: Synthesis and Physicochemical and Photoactivity Studies.

Abstract

The autocyclotetramerization of the precursor 2,3-dicyano-5,6-di(2'-pyridyl)pyrazine [(CN)2Py2Pyz] in the presence of MCl3 compounds (M = AlIII, GaIII) leads to the formation of the new mononuclear porphyrazine complexes [Py8TPyzPzMCl]·xH2O (Py8TPyzPz = tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato anion). From these species, the hydroxide analogues [Py8TPyzPzMOH]·xH2O were obtained by contact with hot water, and their corresponding pentanuclear species [(PdCl2)4Py8TPyzPzMCl]·xH2O could be easily formed by the reaction with PdCl2. Physicochemical characterization of the mono- and pentanuclear macrocycles was based on elemental analysis, and mass, powder X-ray, and IR spectra. UV-vis spectral studies of the mononuclear species in solutions of DMF, DMSO, or pyridine (c ≈ 10-5-10-6 M) indicate (mainly in DMF and DMSO) the initial presence of aggregation, in some cases accompanied by the concomitant occurrence for the complex of a one-electron reduction. While disaggregation into a single species evolves spontaneously over time, the -1 charged species, eventually also found present, can be brought back to its neutral form by addition of a slight amount of HCl, the final spectrum showing the presence of the starting neutral species in its pure monomeric form. Similar aspects were faced also for the parent pentanuclear complexes. Cyclic voltammetry experiments, conducted for the mono-/pentanuclear complexes in DMF and DMSO (c ≈ 10-4 M), exhibit progressive one-electron reductions (1 → 4) characterized by E1/2 values (V vs SCE) positioned to significantly less negative values than those known for the phthalocyanine (Pc) analogues, these data confirming the previously already proven higher electron-deficient character of the MII derivatives of the Py8TPyzPz macrocycle with respect to Pc. The role of the present new series of AlIII and GaIII macrocyclic species to act as photosensitizers for the generation of singlet oxygen, 1O2, the cytotoxic agent in the anticancer treatment known as photodynamic therapy (PDT), has been explored in DMF/HCl. Among the quantum yields ΦΔ, the value found for the GaIII complex [Py8TPyzPzGaCl] (0.68), practically coincident with that observed for the TTDPz analogue (0.69), is well above those of most porphyrazines analogues (ΦΔ = 0.4-0.6), a result encouraging further research work for potential applications in the biochemical field.