Oligoamide Foldamers as Helical Chloride Receptors : the Influence of Electron-Withdrawing Substituents on Anion-Binding Interactions
Helttunen, K., Annala, R., Suhonen, A., Iloniemi, J., Kalenius, E., Aragay, G., Ballester, P., Tuononen, H., & Nissinen, M. (2019). Oligoamide Foldamers as Helical Chloride Receptors : the Influence of Electron-Withdrawing Substituents on Anion-Binding Interactions. Chemistry : An Asian Journal, 14(5), 647-654. https://doi.org/10.1002/asia.201801869
Published inChemistry : An Asian Journal
DisciplineEpäorgaaninen ja analyyttinen kemiaOrgaaninen kemiaNanoscience CenterInorganic and Analytical ChemistryOrganic ChemistryNanoscience Center
© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
The anion‐binding properties of three closely related oligoamide foldamers were studied using NMR spectroscopy, isothermal titration calorimetry and mass spectrometry, as well as DFT calculations. The 1H NMR spectra of the foldamers in [D6]acetone solution revealed partial preorganization by intramolecular hydrogen bonding, which creates a suitable cavity for anion binding. The limited size of the cavity, however, enabled efficient binding by the inner amide protons only for the chloride anion resulting in the formation of a thermodynamically stable 1:1 complex. All 1:1 chloride complexes displayed a significant favourable contribution of the entropy term. Most likely, this is due to the release of ordered solvent molecules solvating the free foldamer and the anion to the bulk solution upon complex formation. The introduction of electron‐withdrawing substituents in foldamers 2 and 3 had only a slight effect on the thermodynamic constants for chloride binding compared to the parent receptor. Remarkably, the binding of chloride to foldamer 3 not only produced the expected 1:1 complex but also open aggregates with 1:2 (host:anion) stoichiometry. ...
PublisherWiley - VCH Verlag GmbH & Co. KGaA
Publication in research information system
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Research Fellow, AoF; Research post as Academy Research Fellow, AoF
Additional information about fundingFunding from Academy of Finland (projects 257246, 284562, 278743 and 312514) and University of Jyvaskyla (mobility funding for KH) are acknowledged. M.Sc. Esa Haapaniemi is gratefully acknowledged for assistance with the NMR measurements and Minna Kortelainen and Anniina Aho for providing foldamer 2.
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