We describe in this paper a study of the equilibrium binding of Zn2+ to the binary mixtures of tridentate terpy-type ligands 1-3, leading to the formation of the dynamic mixture of homo- (4-6) and hetero- (7-9) coordination compounds. We report the crystal structures of five such complexes (4, 5, 7-9) which assemble into complementary duplex compounds, and further selforganize into double helical- or lamellar-type architectures in the solid state.