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An Integrated Approach (Thermodynamic, Structural, and Computational) to the Study of Complexation of Alkali-Metal Cations by a Lower-Rim Calix[4]arene Amide Derivative in Acetonitrile

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Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Laboratory of Supramolecular and Nucleoside Chemistry, Department of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, Croatia
Cite this: Inorg. Chem. 2012, 51, 11, 6264–6278
Publication Date (Web):May 9, 2012
Copyright © 2012 American Chemical Society

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    The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M+ (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C2 point group) of L was generally more favorable than the square cone conformation (C4 point group). In the complex with Na+, L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C2 to C4 symmetry. As in solution studies, in the case of ML+ complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone conformation to bind the solvent molecule, allowing it to more easily and faster enter the calixarene cavity.

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    X-ray crystallographic data in CIF format, ORTEP plots and packing diagrams, experimental and calculated 1H and 13C NMR chemical shifts of compound L, temperature dependence of 1H NMR spectra of L in CDCl3 and CD3CN, results of 1H NMR titrations of L with LiClO4, NaClO4 and KClO4 in CD3CN and 1H NMR titrations of L and [NaL]ClO4 with MeCN in CDCl3, additional results of spectrophotometric, conductometric, and microcalorimetric titrations, and additional results of MD simulations. This material is available free of charge via the Internet at

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