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• W1782854067 abstract "Abstract N , N′ ‐Bis(triazolyl)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 1 H and 13 C NMR spectroscopy. The solid‐state structure of Ni II and Zn II complexes formed by the diaza[18]crown‐6 ligand were determined by means of X‐ray crystallography. The Ni II complex is centrosymmetric; 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 II –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 two N atoms of the triazolyl motifs on the pendant arms occupy the axial positions. The diamagnetic character of the Zn II ion allows its structural study in solution by NMR spectroscopy. A dynamic behavior was observed at room temperature, which corresponds to the displacement of the Zn II ion between the bond end and the nonbond end of the macrocycle. This movement results in an S 4 ‐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 irregular octahedral coordination modes, respectively. Only the structure of the Cu II complex with N , N′ ‐bis(triazolyl)diaza[15]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." @default.
• W1782854067 created "2016-06-24" @default.
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• W1782854067 date "2014-08-29" @default.
• W1782854067 modified "2023-10-17" @default.
• W1782854067 title "Evolution of the Coordination‐Sphere Symmetry in Copper(II), Nickel(II), and Zinc(II) Complexes with <i>N</i> , <i>N′</i> ‐Double‐Armed Diaza‐Crown Ethers: Experimental and Theoretical Approaches" @default.
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• W1782854067 doi "https://doi.org/10.1002/ejic.201402432" @default.
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