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The importance of detailed thermodynamic studies in assessing the selective behaviour ofmacrocyclic receptors for one species relative to another in a given solvent and the medium effect oncomplexation processes involving ionic species are emphasised. Factors to be considered in the determinationof thermodynamic parameters of complexation in non-aqueous solvents are highlighted. Particularreference is made to the need for considering the bulk of information available in the literature on the solutionproperties of electrolytes in non-aqueous medium in the selection of the solvent for ioncomplexation processes involving macrocycles.A detailed thermodynamic study on the interaction of p-tert-butyl calix[n]arene (n = 4−6) tertiary amidederivatives with uni- and bivalent cations in protic (methanol) and dipolar aprotic (acetonitrile) media isreported. It is demonstrated that as the number of phenyl units in the macrocycle increases, the vital featureof the cyclic tetramer receptor for selective recognition of cations decreases significantly for the cyclicpentamer and almost disappears for the hexamer. Concluding remarks are included. (doi:10.5562/cca2170

An Enchiridion of Supramolecular Thermodynamics: Calix[N]arene (N=4,5,6) Tertiary Amide Derivatives and their Ionic Recognition