A new dirhodium complex containing an extended π-system, cis-H,H-[Rh2(OCCH3NH)2(dppn)(CH3CN)2]2+ (dppn = benzo-dipyrido[3,2-a:2’,3’-c]phenanzine), was synthesized in order to increase the intercalative DNA binding upon photoactivation. The dppn ligand, which serves as a DNA base pair intercalator, chelates to one Rh atom and is positioned trans to the amidato N atoms of the bridging acetamide ligand. Visible light irradiation in water leads to the displacement of one equivalence of CH3CN for a H2O molecule, producing cis-H,H-[Rh2(OCCH3NH)2(dppn)(H2O)(CH3CN)]2+. This unique photoproduct was expected to interact with DNA via intercalation through the dppn moiety and covalent binding by displacement of the labile water molecule by the DNA bases. In addition, because dppn is known to sensitize the production of singlet oxygen (1O2), the photophysical properties of cis-H,H-[Rh2(OCCH3NH)2(dppn)(CH3CN)2]2+ with DNA were explored. The interactions of the complex with DNA in the dark and when irradiated will be discussed.

New dirhodium (II,II) complex with potential dual-binding to DNA upon photoactivation

249th National Meeting (2015)

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