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Issue 36, 2017
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How the electron-deficient cavity of heterocalixarenes recognizes anions: insights from computation

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Abstract

We have quantum chemically analyzed the bonding mechanism behind the affinity of various heterocalixarenes for anions with a range of geometries and net charges, using modern dispersion-corrected density functional theory (DFT-D3BJ). The purpose is to better understand the physical factors that are responsible for the computed affinities and thus to develop principles for a more rational design of anion receptors. Our model systems comprise heterocalixarenes 1–4 as hosts, which are characterized by different bridging heteroatoms (O, N, S) as well as the anionic guests Cl, Br, I, BF4, CH3CO2, H2PO4, HSO4, NCS, NO3, PF6, and SO42−. We use various analysis schemes (EDA, NCI, and NBO) to elucidate the interactions between the calixarene cavity and the anions to probe the importance of the different bonding modes (anion–π, lone-pair electron-π, σ-complexes, hydrogen bonds, and others) of the interactions. Electrostatic interactions appear to be dominant for heterocalixarenes with oxygen bridges whereas orbital interactions prevail in the case of nitrogen and sulfur bridges. Dispersion interactions are however in all cases non-negligible.

Graphical abstract: How the electron-deficient cavity of heterocalixarenes recognizes anions: insights from computation

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Publication details

The article was received on 12 Jun 2017, accepted on 14 Aug 2017 and first published on 14 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP03925E
Citation: Phys. Chem. Chem. Phys., 2017,19, 24696-24705
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    How the electron-deficient cavity of heterocalixarenes recognizes anions: insights from computation

    A. O. Ortolan, G. F. Caramori, F. Matthias Bickelhaupt, R. L. T. Parreira, A. Muñoz-Castro and T. Kar, Phys. Chem. Chem. Phys., 2017, 19, 24696
    DOI: 10.1039/C7CP03925E

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