Competing Hydrogen-Bond Polarities in a Dynamic Oligourea Foldamer: A Molecular Spring Torsion Balance
| Autor: | Jonathan Clayden, John W. Ward, Matej Žabka, Romina Wechsel |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
education.field_of_study
010405 organic chemistry Chemistry Hydrogen bond Population Intermolecular force Foldamer Molecular spring Hydrogen Bonding General Chemistry Molecular Dynamics Simulation 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Crystallography Molecular dynamics Colloid and Surface Chemistry Intramolecular force Urea education Conformational isomerism |
| Zdroj: | Wechsel, R, Ward, J W, Clayden, J & Zabka, M 2018, ' Competing Hydrogen-Bond Polarities in a Dynamic Oligourea Foldamer : A Molecular Spring Torsion Balance ', Journal of the American Chemical Society, vol. 140, no. 10, pp. 3528-3531 . https://doi.org/10.1021/jacs.8b00567 |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.8b00567 |
| Popis: | Symmetrical oligourea foldamers were made from meso cyclohexane-1,2-diamine and desymmetrised by incorporating terminal functional groups (carbamates, ureas or thioureas) with differing hydrogen-bonding capacities. Irrespective of solvent, the foldamers populate a dynamic equilibrium of two alternative screw-sense conformers whose relative population is determined by the competing hydrogen-bonding properties of the terminal groups, dictating the foldamer's global hydrogen-bond directionality. Intermolecular association of these dynamic foldamers with achiral anionic guests (acetate or phosphate, but not neutral hydrogen-bonding solvents) leads to inversion of the conformational preference, as strong intermolecular hydrogen bonding induces reorganization of the intramolecular hydrogen-bond network. The foldamers behave as a molecular torsion balance whose conformational preference is governed by competing hydrogen-bond pairing. |
| Databáze: | OpenAIRE |
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