Intramolecular van der Waals Interactions Challenge Anion Binding in perthio-Bambusurils

Pravat Mondal, Ephrath Solel, Natalia Fridman, Ehud Keinan, Ofer Reany

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

Bambusurils (BUs) are known to be rigid cavitands that feature an extended, jigger-like conformation, and the BU[6]s strongly bind anions within their hydrophobic cavity. These features are not necessarily shared by the family of perthio-BUs. This study reveals that perthio-BUs assume a compact conformation and perthio-BU[6]s are poor anion binders, crystallizing as anion-free species from solutions containing halide salts. Computational studies show that the equatorial sulfur atoms compete against guest anions for binding with the glycoluril methine groups via strong van der Waals (vdW) attractive interactions. These competitive contacts not only account for the diminished anion-binding of perthio-BUs, but also explain their compact conformation. The semithio- and perthio-BU[4]s form linear coordination polymers with HgII in the solid-state regardless of their intrinsic molecular conformation. The strong involvement of sulfur atoms in intramolecular interactions differentiates the equatorial from the axial (peripheral) heteroatoms, thus offering chemoselective and regioselective transformations.

Original languageEnglish
Pages (from-to)13336-13343
Number of pages8
JournalChemistry - A European Journal
Volume25
Issue number58
DOIs
StatePublished - 17 Oct 2019
Externally publishedYes

Keywords

  • anion receptors
  • bambusuril
  • cavitands
  • host–guest chemistry
  • sulfur ligands

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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