title: Stereoelectronic effects: a simple yet powerful tool to manipulate anion affinity.
abstract: Different strategies are employed in designing strong and selective anion receptors but stereoelectronic effects have been largely ignored. In this work, the stereo configuration of a non-interacting ether is found to have a large impact of more than two orders of magnitude on the binding of a rigid diol with tetrabutylammonium chloride in acetonitrile-d3. A favorable carbon-oxygen dipole and an intramolecular C-HOH hydrogen bond in an equatorially substituted ether is found to be energetically more important than a stabilizing hydrogen bond in the corresponding axially oriented alcohol. IR spectroscopy is also used to probe the structures of the bound complexes and several binding motifs are identified.
authors.affiliation: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA. kass@umn.edu.
authors.forename: Masoud
authors.initials: M
authors.lastname: Samet
authors.forename: Alireza
authors.initials: A
authors.lastname: Fattahi
authors.forename: Steven R
authors.initials: SR
authors.lastname: Kass
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D004987:Ethers / Q000737:chemistry*; D006860:Hydrogen Bonding; D015394:Molecular Structure; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000097:Acetonitriles; D000838:Anions; D004987:Ethers; D000644:Quaternary Ammonium Compounds; C009405:tetrabutylammonium; C032159:acetonitrile