Abstract
Following an overview in the field of Supramolecular Chemistry given in the Introduction, this thesis reports and discusses i) The synthesis of 5,11,17,23 tetra-tert-butyl, 25,27 bis(diethylphosphate amino) ethoxy, 26,28 dihydroxycalix[4]arene, 1, and 5,11,17,23 tetra-tert-butyl, 25,27-bis(diethylthiophosphate amino) ethoxy, 26,28 dihydroxy-calix[4]arene, 2, and their characterization by 1H and 13C NMR, elemental analysis and X-ray crystallography. ii) The solution thermodynamics of 1 and 2 in various solvents at 298.15 K and the transfer thermodynamics of these ligands from acetonitrile to various solvents. iii) Electrochemical (conductance) studies on the interaction of 1 and 2 and metal cations in acetonitrile, methanol and in the water-dichloromethane solvent system at 298.15 K. Conductance measurements were used to establish the composition of the metal-ion complexes in various solvents. iv) Calorimetric and potentiometric measurements performed for the derivation of the thermodynamics associated with the complexation process in acetonitrile and methanol. These measurements were carried out to establish the selective behaviour of 1 and 2 for a given cation relative to another in these solvents. v) Distribution experiments in the absence and in the presence of 2 with different metal cations in the water-dichloromethane solvent system at 298.15 K. These measurements were used to derive partition, association, distribution and extraction equilibria data in this solvent system. vi) The attachment of 2 into a polymeric framework and the capacity of the new material to extract mercury(II) salts from aqueous solutions. Recycling of the polymeric material was successfully achieved. Suggestions for further work in this area are given.