Ligand substitution reactions supramolecular chemistry

Solvent free methods have been used extensively in supramolecular chemistry, coordination chemistry and the formation of transition metal clusters and polymers. Reactions range from very simple ligand substitution reactions for salts of labile metal ions to more complex procedures, some of which are outlined below. 

Synthetic developments in the area of Supramolecular Chemistry are currently leading to a massive production of new macrocycles. The driving force for this continuous growth is the search for selective hosts to target a particular neutral or ionic species. There is no doubt that the impact produced by the discovery of macrocyclic ligands such as the crown ethers [1] and the cryptands [2] resulted from their cation complexation and this prompted us to consider the thermodynamic characterisation of these systems (mainly cryptands) which has been extensively reported [3-5]. Calixarenes, an important class of macrocyclic compounds, are products of the base-catalysed condensation reaction of p-substituted phenols and formaldehyde [6, 7]. These compounds are characterised by their low solubilities in most solvents, although until recently [8], no quantitative data has been reported. Functionalisation of the lower or upper rim of parent calix[n]arenes has... 

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