Journal
DALTON TRANSACTIONS
Volume 40, Issue 32, Pages 8059-8071Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1dt10055f
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Funding
- Swiss National Science Foundation
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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.
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