title: Computational and Experimental Evidence of Emergent Equilibrium Isotope Effects in Anion Receptor Complexes.
abstract: The measurement of a deuterium equilibrium isotope effect (EIE) for the aryl CH···Cl-interaction of anion receptor 1H/1D is reported. Computations corroborate the results of solution measurements for a small, normal EIE in the full complex (KaH/KaD= 1.019 ± 0.010). Interestingly, isotope effects involving fragments of the anion receptor (urea, aryl ring, etc.) are predicted to produce an inverse effect. This points to an unusual and subtle structural organization effect of the anion receptor complex that changes the nature of the combined interactions to a normal isotope effect. The reversal of EIE values suggests that overall architecture of the anion receptor can dramatically impact the nature of bonding in these complexes.
authors.affiliation: Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon , Eugene, Oregon 97403-1253, United States.
authors.forename: Blakely W
authors.initials: BW
authors.lastname: Tresca
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Alexander C
authors.initials: AC
authors.lastname: Brueckner
authors.affiliation: Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon , Eugene, Oregon 97403-1253, United States.
authors.forename: Michael M
authors.identifier: 0000-0002-7027-4141
authors.initials: MM
authors.lastname: Haley
authors.affiliation: Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
authors.forename: Paul H-Y
authors.initials: PH
authors.lastname: Cheong
authors.affiliation: Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon , Eugene, Oregon 97403-1253, United States.
authors.forename: Darren W
authors.identifier: 0000-0001-5967-5115
authors.initials: DW
authors.lastname: Johnson
mesh_terms: D000838:Anions / Q000737:chemistry; D066241:Carbon-13 Magnetic Resonance Spectroscopy; D003903:Deuterium / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D000838:Anions; D006859:Hydrogen; D003903:Deuterium