Synthesis, structure and DNA-binding studies of tetranuclear copper(II) complexes bridged by asymmetrical N,N′-bis(substituted)oxamides

Two tetranuclear copper(II) complexes bridged by asymmetrical N,N′-bis(substituted)oxamides have been synthesized and characterized as [Cu4(dmapob)2(Me2bpy)2](pic)2·6H2O (1) and [Cu4(oxbe)2(dabt)2](pic)2 (2), where H3dmapob and H3oxbe denote N-benzoato-N′-[3-(dimethylamino)propyl]oxamido and N-benzoato-N′-(2-aminoethyl)oxamide, respectively; and Me2bpy, dabt, and pic represent 4,4′-dimethyl-2,2′-bipyridine 2,2′-diamino-4,4′-bithiazole, and 2,4,6-trinitrophenol, respectively. Complex 1 was characterized by elemental analyses, IR and electronic spectra, and single-crystal X-ray diffraction. Its structure consists of two asymmetrical binuclear copper(II) units linked by carboxyl bridges into a circular tetranuclear copper(II) complex with an embedded center of inversion. The copper(II) centers are in square-planar and distorted square-pyramidal environments. Hydrogen bonds and aromatic stacking interactions link the tetranuclear copper(II) fragments into a 3D supramolecular structure. The interactions of complexes 1 and 2 with herring sperm DNA (HS-DNA) were investigated by electronic and fluorescence spectra and viscosity measurements. Both complexes bind to HS-DNA via the intercalative mode, and complex 2 displays a significant binding propensity to HS-DNA.