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

Author(s)

Ortolan, Alexandre O. ^[1] ; Caramori, Giovanni F. ^[1] ; Matthias Bickelhaupt, F. ^{[2, 3, 4]} ; Parreira, Renato L. T. ^[5] ; Munoz-Castro, Alvaro ^{[6, 7]} ; Kar, Tapas ^[8]

Affiliation

^[1] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil

^[2] Vrije Univ Amsterdam, Dept Theoret Chem, De Boelelaan 1083, NL-1081 HV Amsterdam - Netherlands

^[3] Vrije Univ Amsterdam, ACMM, De Boelelaan 1083, NL-1081 HV Amsterdam - Netherlands

^[4] Radboud Univ Nijmegen, Inst Mol & Mat, Heyendaalseweg 135, NL-6525 AJ Nijmegen - Netherlands

^[5] Univ Franca, Nucleo Pesquisa Ciencias Exatas & Tecnol, BR-14404600 Franca, SP - Brazil

^[6] Univ Autonoma Chile, Lab Quim Inorgan & Mat Mol, Llano Subercaceaux 2801, Santiago - Chile

^[7] Univ Andres Bello, Fisicoquim Mol, Av Republ 275, Santiago 8370146 - Chile

^[8] Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 - USA

• Document type: Journal article
• Source: Physical Chemistry Chemical Physics; v. 19, n. 36, p. 24696-24705, SEP 28 2017.
• Web of Science Citations: 10

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 dispersioncorrected 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-, CH3 CO2-, 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-pi, lone-pair electron-pi, s-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. (AU)

• FAPESP's process: 11/07623-8 - The use of quantum-mechanical methods to study the bonds and chemical interactions in self-organizing systems with applications in catalysis, medicinal chemistry, electrochromism, energy storage and conversion
• Grantee: Renato Luis Tame Parreira
• Support Opportunities: Research Grants - Young Investigators Grants