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Synthesis, Characterization and Anticancer Activity of Porphyrin-Containing Organometallic Cubes
Auteur(s)
Date de parution
2010
In
Australian Journal of Chemistry, CSIRO, 2010/63/11/1529-1537
Résumé
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 <i>p</i>-cymene ruthenium clips [Ru<sub>2</sub>(<i>p</i>-cymene)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)Cl<sub>2</sub>] and [Ru<sub>2</sub>(<i>p</i>-cymene)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)Cl<sub>2</sub>] (C<sub>2</sub>O<sub>4</sub> = oxalato; C<sub>6</sub>H<sub>2</sub>O<sub>4</sub> = 2,5-dioxydo-1,4-benzoquinonato) affords the cationic organometallic cubes: [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-H<sub>2</sub>)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>1</b>); [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-Ni)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>2</b>); [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-Zn)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>3</b>); [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-H<sub>2</sub>)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>4</b>); [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-Ni)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>5</b>); and [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-Zn)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>6</b>). In addition, the new dinuclear arene ruthenium 2,5-dioxydo-1,4-benzoquinonato clips [Ru<sub>2</sub>(indane)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)Cl<sub>2</sub>] (<b>7</b>) and [Ru<sub>2</sub>(nonylbenzene)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)Cl<sub>2</sub>] (<b>8</b>) react in methanol with tpp-H<sub>2</sub> in the presence of silver triflate to afford the corresponding cationic cubes [Ru<sub>8</sub>(indane)<sub>8</sub>(tpp-H<sub>2</sub>) <sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>9</b>) and [Ru<sub>8</sub> (nonylbenzene)<sub>8</sub>(tpp-H<sub>2</sub>)<sub>2</sub>(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>10</b>) 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, [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-H<sub>2</sub>)(tpp-Ni)(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>11</b>), [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-H<sub>2</sub>)(tpp-Zn)(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>12</b>), and [Ru<sub>8</sub>(<i>p</i>-cymene)<sub>8</sub>(tpp-Ni)(tpp-Zn)(C<sub>6</sub>H<sub>2</sub>O<sub>4</sub>)<sub>4</sub>]<sup>8+</sup> (<b>13</b>), 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.
Identifiants
Type de publication
journal article
