Solvation Effects in Supramolecular Chemistry

Solvation plays diverse significant roles in supramolecular assembly processes. Interaction of solvent molecules with host, guest, and their complex is a critical function of the size, shape, and functionality of each component, as well as the nature of solvent. The thermodynamic parameters obtained for the complexation of a series of host–guest combinations in various solvents often exhibit a compensatory enthalpy–entropy relationship, analysis of which provides a powerful tool for globally understanding the mechanisms operative in supramolecular complexation and solvent reorganization. This article first presents some theoretical considerations, illustrates the crucial roles played by solvation and desolvation upon supramolecular complexation by using representative host–guest–solvent systems, and finally provides clues for practical applications and future perspective.