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

Ortolan A.O.; Caramori G.F.; Matthias Bickelhaupt F.; Parreira R.L.T.; Muñoz-Castro A.; Kar T.

dc.contributor.author	Ortolan A.O.
dc.contributor.author	Caramori G.F.
dc.contributor.author	Matthias Bickelhaupt F.
dc.contributor.author	Parreira R.L.T.
dc.contributor.author	Muñoz-Castro A.
dc.contributor.author	Kar T.
dc.date.accessioned	2020-09-02T22:25:09Z
dc.date.available	2020-09-02T22:25:09Z
dc.date.issued	2017
dc.identifier	10.1039/c7cp03925e
dc.identifier.citation	19, 36, 24696-24705
dc.identifier.issn	14639076
dc.identifier.uri	https://hdl.handle.net/20.500.12728/5674
dc.description	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. © 2017 the Owner Societies.
dc.language.iso	en
dc.publisher	Royal Society of Chemistry
dc.title	How the electron-deficient cavity of heterocalixarenes recognizes anions: Insights from computation
dc.type	Article

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

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