Ternary Dinuclear Copper(II) Complexes of a Hydroxybenzamide Ligand with Diimine Coligands: the 5,6-dmp Ligand Enhances DNA Binding and Cleavage and Induces Apoptosis

The dinuclear copper(II) complexes [Cu2(LH)2(diimine)2(ClO4)2](ClO4)2 (1–4), where LH = 2-hydroxy-N-[2-(methylamino)ethyl]benzamide and diimine = 2,2′-bipyridine (bpy; 1), 1,10-phenanthroline (phen; 2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp; 3), and dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq; 4), have been isolated and characterized. The X-ray crystal structure of complex 1 contains two copper(II) centers bridged by the phenolate moiety of the amide ligand. All of the complexes display a ligand-field band (630–655 nm) and the PhO–-to-CuII ligand-to-metal charge-transfer band (405–420 nm) in solution. Absorption and emission spectral studies and viscosity measurements indicate that complex 4 interacts with calf thymus DNA more strongly than all of the other complexes through strong partial intercalation of the extended planar ring (dpq) with a DNA base stack. Interestingly, 3 exhibits a DNA binding affinity higher than 2, suggesting the involvement in hydrophobic interaction of coordinated 5,6-dmp with th...