Cationic CHπ interactions as a function of solvation

Bright U Emenike; Sara N Bey; Ronald A Spinelle; Jacob T Jones; Barney Yoo; Matthias Zeller

doi:10.1039/c6cp06800f

Cationic CHπ interactions as a function of solvation

Phys Chem Chem Phys. 2016 Nov 16;18(45):30940-30945. doi: 10.1039/c6cp06800f.

Authors

Bright U Emenike¹, Sara N Bey¹, Ronald A Spinelle¹, Jacob T Jones¹, Barney Yoo², Matthias Zeller³

Affiliations

¹ Department of Chemistry & Physics, State University of New York, 223 Store Hill Road, Old Westbury, NY 11568, USA. emenikeb@oldwestbury.edu.
² Department of Chemistry, Hunter College, City University of New York, New York, NY 10065, USA.
³ Department of Chemistry, Purdue University, West Lafayette, IN 47907-2084, USA.

PMID: 27781222
DOI: 10.1039/c6cp06800f

Abstract

The energy (ΔG) of a cationic CHπ interaction was measured experimentally through the conformational studies of new molecular torsion balances using proton NMR spectroscopy. Each of the molecular balance adopted folded and unfolded conformations for which the ratio of the conformational equilibrium (i.e., folded/unfolded ratio) provided a quantitative measure of the ΔG as a function of solvation. An excellent linear solvation energy relationship between the ΔG values and the Hunter's solvent hydrogen-bond parameters (α_s and β_s) revealed that electrostatic interaction is the physical origin of the observed conformational preferences in solution.