Functional group interaction profiles: a general treatment of solvent effects on non-covalent interactions

Abstract

Functional group interaction profiles are a quantitative tool for predicting the effect of solvent on the free energy changes associated with non-covalent interactions.

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

“… 89 The group of Hunter showed that, contrasting to such bimodal solvent dependencies, local effects due to high effective molarities may be independent of the solvent polarity. 90 , 91 Despite the complexity of many interactions driving supramolecular complexation, interaction strength and solvent dependency can be calculated rather straightforwardly 92 , 93 using literature-derived parameters. 94 As such, solvation influences supramolecular aggregation in numerous ways and many cooperative effects can emerge.…”

Solvent similarity index

“…The SSIP representation of 261 solvent molecules was described previously (see ESI † for full list of solvents). 67 These representations were used to calculate solvation free energies for all solute SSIP values between À10 and +5 in increments of 0.1. Plotting the results gives a unique solvation profile for each solvent, which describes the non-covalent interactions the solvent would make with any solute taking into account the polarity and the concentration of the interaction sites present in the solvent.…”

An empirical model for solvation based on surface site interaction points

“…As we have previously suggested, the constant of 6 kJ mol À1 in eqn ( 1) is related to the difference between the concentration of the solvent and the standard state of 1 M used to describe the chemical potentials of the solutes. 21,25 Fig. 3 shows experimental data for formation of a 1 : 1 H-bonded complexes in various ether solvents.…”