Issue 36, 2017

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

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

Supplementary files

Article information

Article type
Paper
Submitted
12 Jun 2017
Accepted
14 Aug 2017
First published
14 Aug 2017

Phys. Chem. Chem. Phys., 2017,19, 24696-24705

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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