Dissecting Solvent Effects on Hydrogen Bonding

Nicole Meredith, Stefan Borsley, Ivan Smoliar, Gary Nichol, Christopher Baker, Kenneth Ling, Scott L Cockroft*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The experimental isolation of H-bond energetics from the typically dominant influence of the solvent remains challenging. Here we use synthetic molecular balances to quantify amine/amide H-bonds in competitive solvents. Over 200 conformational free energy differences were determined using 24 H-bonding balances in 9 solvents spanning a wide polarity range. The correlations between experimental interaction energies and gas-phase computed energies exhibited wild solvent-dependent variation. However, excellent correlations were found between the same computed energies and the experimental data following empirical dissection of solvent effects using Hunter’s α/β solvation model. In addition to facilitating the direct comparison of experimental and computational data, changes in the fitted donor and acceptor constants reveal the energetics of secondary local interactions such as competing H-bonds.
Original languageEnglish
JournalAngewandte Chemie International Edition
Early online date24 May 2022
DOIs
Publication statusE-pub ahead of print - 24 May 2022

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