Thermodynamics and mechanisms of the formation of supramolecules and supramolecular assemblies of s, p, d and f elements: problems and prospects

The experimental results concerning the mechanism and thermodynamics of formation of three classes of supramolecular systems, namely, polymers, discrete ring nanostructures and macrocyclic complexes (with crown ethers, cryptands, etc.) are surveyed. The thermodynamic factors, in particular, the bond energy between the 'building blocks', determining the stability of supramolecular assemblies are analysed. The energy contributions of the metal–ligand and metal–metal interactions and hydrogen bonds to the thermodynamics and mechanism of self-assembly are compared. The principles of design of new polynuclear assemblies of s, p, d and f elements are considered.