Abstract
Solvation has profound effects on the behaviour of supramolecular systems, but the effects can be difficult to predict even at a qualitative level. Functional group interaction profiles (FGIPs) provide a simple visual method for understanding how solvent affects the free energy contribution due to a single point interaction, such as a hydrogen bond, between two solute functional groups. A generalised theoretical approach has been developed, which allows calculation of FGIPs for any solvent or solvent mixture, and FGIPs for 300 different solvents have been produced, providing a comprehensive description of solvent effects on non-covalent chemistry. The free energy calculations have been validated using experimental measurements of association constants for hydrogen bonded complexes in multiple solvent mixtures. The calculated FGIPs provide good descriptions of the solvation of polar solutes, solvophobic interactions between non-polar solutes in polar solvents like water, and preferential solvation in solvent mixtures. Applications are explored of the use of FGIPs in drug design, for optimising receptor-ligand interactions, and in enantioselective catalysis for solvent selection to optimise selectivity.
Highlights
Solvation plays an essential role in a wide range of different condensed phase phenomena
Experimental measurements of solvent effects on the stabilities of hydrogen bonded complexes have shown that hydrogen bond parameters determined for isolated molecules generally provide a good description of the corresponding solvent parameters, i.e. the hydrogen bond parameters for a speci c molecule are independent of whether the molecule is the acting as the solvent or solute.[36]
The original formulation of the Functional group interaction profiles (FGIPs) was limited to simple solvents, because solvation was described as interaction with a single type of solvent hydrogen donor and a single type of solvent hydrogen bond acceptor.[19]
Summary
Solvation plays an essential role in a wide range of different condensed phase phenomena. The rst term in eqn (1) represents the free energy change associated with the exchange of polar interactions between solutes and solvent Expressing this energy as DDGFGI in eqn (2) provides a useful tool for predicting the free energy contribution that a speci c functional group interaction makes to the stability of a supramolecular system where there are multiple non-covalent interactions. If the solvent–solvent interaction is the most stable of the four species, the equilibrium will lie to the right, i.e. when a < aS and b < bS, DDGFGI will be negative We develop a generalised treatment that allows calculation of FGIPs for any solvent composition and illustrate the power of the approach by providing FGIPs for about 300 different solvents and solvent mixtures
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