A Half-Century of Supramolecular Thermodynamics: A Retrospective of Our Multidisciplinary Approach

This review synthesizes 50 years of thermodynamic research in supramolecular chemistry, focusing on the interactions of diverse receptors with ionic and neutral species across various media. By evaluating a selection of foundational publications, this work highlights the critical role of host–guest selectivity. Crucially, we emphasize that a deep understanding of fundamental thermodynamics, including binding constants, enthalpy, and entropy changes, is essential to rationally guide and optimize practical applications. In doing so, we used nuclear magnetic resonance (NMR), ultraviolet-visible (UV-Vis) spectroscopy, conductometry, potentiometry and titration microcalorimetry to characterize solution processes. We consider the scope and limitations of these techniques as well as the inherent limitations of the reaction media. We analyze how solution studies correlate with solid state profiles derived from X-ray diffraction (XRD) scanning electron microscopy (SEM), energy dispersive atomic X-ray spectroscopy (EDAX), thermogravimetric analysis and infrared (IR) spectroscopy. This foundational knowledge bridges theory and practice, driving applications in environmental remediation, such as targeted pollutant removal, and the development of highly sensitive, on-site sensing devices for real-time water monitoring. Finally, based on the historical trends and current gaps identified in the selected literature, we offer strategic suggestions for further research in this area.