Synthesis, characterization, spectrophotometric and electrochemistry studies, and DNA cleavage of copper(II) complexes of a new azacrown bis-macrocycle and its mono-cyclic analogue

A new azacrown bis-macrocycle (5) and its mono-cyclic analogue (7) were synthesized and characterized by FT-IR, H-1 NMR, C-13 NMR, DEPT C-13 NMR, MS, and elemental analysis. The reaction with copper(II) nitrate yielded the corresponding complexes, formulated as Cu(5)(NO3)(2)center dot 3H(2)O (8), and Cu(7)(NO3)(2)center dot 2.5H(2)O (9). Also the stoichiometries of the complexes were determined in alcoholic solution and the results show that for both complexes the ratio of ligand to metal was 1:1 in methanol. The redox behavior of both complexes has been studied by cyclic voltammetry in DMF. Cyclic voltamogram of 8 shows quasi-reversible Cu-II/Cu-I redox couple whereas 9 shows a reversible Cu-II/Cu-I redox couple. Mono-and bis-macrocycle copper(II) complexes (8 and 9 respectively) cleaved plasmid pGS2 DNA by using an oxidative mechanism with 3- mercaptopropionic acid (MPA) as the reductant under aerobic conditions. The bis-macrocycle copper(II) complex 8 showed higher cleavage efficiency than their mono-macrocycle analogue 9 at the same Cu2+ concentration.