The syntheses, characteristics of dinuclear macrocyclic polyamine zinc complexes and their interaction with plasmid DNA are reported. The two cyclen (1,4,7, 10-tetraazacyclododecane) moieties are bridged by rigid and flexible linkages. The crystal structures of Zn2C27H43N8O15Cl4 [5c center dot(ClO4)(3) center dot 2H(2)O] and Zn2C3OH43N10O13Cl3 [5e center dot (ClO4)(3) center dot H2O] have been determined. The complexes crystallize in the monoclinic space group C2/c and P2(1)/c with the following unit cell parameters: 5c center dot (ClO4)3 center dot 21120: a = 32.568(4) angstrom, b = 14.8593(17) angstrom, c = 19.443(2) angstrom, alpha = 90.00 degrees, beta = 119.435(4)degrees, gamma = 90.00 degrees, D-c = 1.551 mg/m(3), FW =956.71, F(000) = 3932; 5e center dot (ClO4)(3) circle H2O: a = 15.807(2)angstrom, b = 16.756(2)angstrom, c = 16.161(2) angstrom, alpha = 90.00 degrees, beta = 97.062(4)degrees, gamma = 90.00 degrees, D-c = 1.546 mg/m(3), FW = 988.83, F(000) = 2032. The distance between the two Zn(II) ions is about 4.0 angstrom. The structures show that two zinc ions can synergistically interact with the substrate DNA. With this novel structural characteristics, the dinuclear macrocyclic polyamine Zn(II) complexes via the synergetic effect between the two zinc ions can catalyze the cleavage of plasmid DNA (pUC18) with unprecedented speed at physiological conditions. (c) 2005 Elsevier Inc. All rights reserved.