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Dissecting Solvent Effects on Hydrogen Bonding.

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.

SUBMITTER: Meredith NY

PROVIDER: S-EPMC9400978 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Dissecting Solvent Effects on Hydrogen Bonding.

Meredith Nicole Y NY Borsley Stefan S Smolyar Ivan V IV Nichol Gary S GS Baker Christopher M CM Ling Kenneth B KB Cockroft Scott L SL

Angewandte Chemie (International ed. in English) 20220614 30

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 ...[more]

PMID: 35608961

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