Faculté des sciences

Synthesis, Characterization and Anticancer Activity of Porphyrin-Containing Organometallic Cubes

Barry, Nicolas P. E. ; Zava, Olivier ; Dyson, Paul J. ; Therrien, Bruno

In: Australian Journal of Chemistry, 2010, vol. 63, no. 11, p. 1529-1537

Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H2) and 5,10,15,20-tetra(4-pyridyl)porphyrin-M(ii) (M = Ni (tpp-Ni); Zn (tpp-Zn)) tetradentate panels with the dinuclear p-cymene ruthenium clips [Ru2(p-cymene)2(C2O4)Cl2] and... Plus

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    Summary
    Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H2) and 5,10,15,20-tetra(4-pyridyl)porphyrin-M(ii) (M = Ni (tpp-Ni); Zn (tpp-Zn)) tetradentate panels with the dinuclear p-cymene ruthenium clips [Ru2(p-cymene)2(C2O4)Cl2] and [Ru2(p-cymene)2(C6H2O4)Cl2] (C2O4 = oxalato; C6H2O4 = 2,5-dioxydo-1,4-benzoquinonato) affords the cationic organometallic cubes: [Ru8(p-cymene)8(tpp-H2)2(C2O4)4]8+ (1); [Ru8(p-cymene)8(tpp-Ni)2(C2O4)4]8+ (2); [Ru8(p-cymene)8(tpp-Zn)2(C2O4)4]8+ (3); [Ru8(p-cymene)8(tpp-H2)2(C6H2O4)4]8+ (4); [Ru8(p-cymene)8(tpp-Ni)2(C6H2O4)4]8+ (5); and [Ru8(p-cymene)8(tpp-Zn)2(C6H2O4)4]8+ (6). In addition, the new dinuclear arene ruthenium 2,5-dioxydo-1,4-benzoquinonato clips [Ru2(indane)2(C6H2O4)Cl2] (7) and [Ru2(nonylbenzene)2(C6H2O4)Cl2] (8) react in methanol with tpp-H2 in the presence of silver triflate to afford the corresponding cationic cubes [Ru8(indane)8(tpp-H2) 2(C6H2O4)4]8+ (9) and [Ru8 (nonylbenzene)8(tpp-H2)2(C6H2O4)4]8+ (10) respectively. All cationic metalla-cubes were isolated as triflate salts and characterized by NMR, infrared, electro-spray mass spectrometry and UV-visible spectroscopy. Moreover, the formation of unsymmetrical metalla-cubes built using a mixture of the different porphyrin panels during the self-assembly of the 2,5-dioxydo-1,4-benzoquinonato metalla-cubes, [Ru8(p-cymene)8(tpp-H2)(tpp-Ni)(C6H2O4)4]8+ (11), [Ru8(p-cymene)8(tpp-H2)(tpp-Zn)(C6H2O4)4]8+ (12), and [Ru8(p-cymene)8(tpp-Ni)(tpp-Zn)(C6H2O4)4]8+ (13), was studied by electro-spray mass spectrometry. The cytotoxicities of all metalla-cubes as well as the mixtures containing the unsymmetrical metalla-cubes were established on human ovarian A2780 and A2780cisR cancer cell lines. All symmetrical compounds are equally cytotoxic (IC50 = 7–15 μM) (IC50 being the drug concentration necessary for 50% inhibition of cell viability) against both A2780 and cisplatin-resistant A2780cisR cancer cells, with stronger cytotoxicities (IC50 = 2–5 μM) observed for the mixtures containing the unsymmetrical 2,5-dioxydo-1,4-benzoquinonato metalla-cubes.