Work

Computational and Experimental Evidence of Emergent Equilibrium Isotope Effects in Anion Receptor Complexes

Year: 2017

Type: article

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.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.7b00612

Authors: Blakely W. Tresca, Alexander C. Brueckner, Michael M. Haley, Paul H.-Y. Cheong, Darren W. Johnson

Institutions: Lawrence Berkeley National Laboratory, University of Oregon, Molecular Foundry, Oregon State University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500