The synthesis and characterization of new polydentate ligand 2-(N),2'-(N')-bis[2-(3-hydroxy-2-oxo-2H-pyridin-1-yl)acetamido]-1(N'),2(N),2'(N')-trimethyl-2,2'-diaminodiethylamine (L3) is reported. The coordination properties of L3 and of two analogous macrocyclic ligands (L1 and L2) toward Cu(II) and Zn(II) metal ions are reported. All three ligands show the 3-hydroxy-2(1H)-pyridinone (HPO) groups attached as sidearms to a polyaza fragment, which is a macrocyclic framework in the case of L1 and L2 while it is an open chain in the case of L3. The role of the polyaza fragments in preorganizing the two sidearms was investigated. The basicity of L3 and the binding properties of L1-L3 were determined by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I = 0.15 mol dm(-3)). UV-vis spectra as well 1H and 13C NMR experiments were used to understand the role of the HPO and of the polyaza fragments in the stabilization of the cations. While L1 forms stable mono- and dinuclear complexes, L2 and L3 can form only mononuclear species with each of the metal ions investigated. In the main mononuclear species of L2 and L3, the two HPO moieties stabilize the M(II) in a square planar geometry due to the two oxygen atoms of each HPO. The coordination sphere of the metal is completed by adding a secondary ligand such as water molecules in the case of Cu(II) systems or OH- in the Zn(II) systems. These results are confirmed by the crystal structures of the [CuH(-1)L2]+ and [CuH(-1)L3]+ species reported herein. Two conformations of L1 can be hypothesized in the formation of the dinuclear species, as suggested by NMR experiments on the [ZnH(-2)L1] species, which shows two conformers slowly interchanging on the NMR time scale, one of which was found to be more insoluble.