title: Enthalpy-entropy correlations as chemical guides to unravel self-assembly processes.
abstract: Intermolecular connections play a crucial role in biology (recognition, signalling, binding), in physics (material cohesion) and in chemistry ((supra)molecular engineering). While a phenomenological thermodynamic free-energy approach for modelling self-assemblies is now at hand, a more satisfying description based on the chemically-intuitive enthalpic and entropic contributions remains elusive. On the other hand, the innumerable reports of empirical enthalpy/entropy correlations characterizing intermolecular interactions justify a questioning about the emergence and exploitation of an apparent 'fourth law of thermodynamics', which could provide a simple manipulation of intermolecular binding processes. This tutorial Perspective aims at highlighting the current level of non-quantum rationalization of enthalpy-entropy correlations and their chemical consequences on the tuning and on the programming of intermolecular interactions in pure materials, and in diluted solutions.
authors.affiliation: Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai Ernest Ansermet, CH-1211, Geneva 4. Claude.Piguet@unige.ch
authors.forename: Claude
authors.initials: C
authors.lastname: Piguet