N,N'-Bis(triazoly)diaza[18]crown-6 and Corresponding diaza[15]crown-5 ethers were synthesized by means of click chemistry. The interaction of these ligands with Ni-II, Cu-II, and Zn-II cations were studied by UV/Vis and H-1 and C-13 NNIR spectroscopy. The solid-state structure of Ni-II and Zu(II) complexes formed by the diaza[18]crown-6 ligand were determined by means of X-ray crystallography. The Ni-II complex is centrosyrnmetric; the geometry around the metal ion is slightly distorted octahedral whereby the equatorial sites were occupied by four N atoms, and the axial positions by two O atoms that come from the crown moiety. For the Zn'' diaza[18]crown-6 complex, an irregular octahedral coordination was observed whereby the metal ion is asymmetrically placed in the macrocyclic cavity. The equatorial plane is occupied by two N and two O atoms of the crown moiety, and to N atoms of the triazolyl motifs on the pendant arms occupy the axial positions. The diamagnetic character of the Zn'' ion allows its structural study in solution by NNIR spectroscopy. A dynamic beh avior was observed at room Lem- perEaure, which coriesporids to the displacement. ion between the bond end and the nonbond end of the macrocycle. This movement results in an S4-symmetrical structure in solution. Quantum chemical calculations at the DFT level have allowed us to interpret the experimental results observed in the solid state for the symmetry of the complexes in terms of covalent and noncovalent interactions, which favor the centrosymmetric and irre. gular octahedral coordination modes, respectively. Only the structure of the Cu-II complex with N,N'-bis(triazolyl)diazal[5]crown-5 ligand has been investigated in the solid state, for which a pentagonal bipyramidal coordination sphere was observed. This coordination geometry was confirmed in solution in MeCN by UV/Vis spectroscopy, and also for the Zn-II complex by NMR spectroscopy. In the case of the Ni-II complex, a structural modification was suggested in solution in MeCN based on the UV/Vis spectrum. The rearrangement of heptadentate coordination to hexadentate is proposed