Abstract
The complexation of cryptand-222 and 18-crown-6 with some alkali metal ions in several dioxane-water solvent mixtures was investigated by a competitive calorimetric titration method. The stabilities of the resulting metal ion complexes in the solvent mixtures are discussed in terms of ligand structural features and preferential solvation properties. The results showed that the macrobicyclic diaza polyether with a three-dimensional cavity has a larger capability than 18-crown-6 to encapsulate ionic species and to screen the interactions between encapsulated cations and solvent molecules. Formation of cryptates was both enthalpy and entropy stabilized, whereas the complexes of 18-crown-6 were only enthalpy stabilized.
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