Open AccessArene-Perfluoroarene Interactions in Solution
Author(s) -
Ga Young Lee,
Elizabeth Hu,
Arnold L. Rheingold,
K. N. Houk,
Ellen M. Sletten
Publication year - 2021
Publication title -
journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.2
H-Index - 228
eISSN - 1520-6904
pISSN - 0022-3263
DOI - 10.1021/acs.joc.1c00921
Subject(s) - chemistry , solvation , intermolecular force , interaction energy , stacking , aqueous solution , computational chemistry , hydrophobic effect , anthracene , intermolecular interaction , solvent , non covalent interactions , titration , london dispersion force , dispersion (optics) , electrostatics , molecule , van der waals force , hydrogen bond , organic chemistry , physics , optics
A systematic study of arene-perfluoroarene interactions in solution is presented. Using a combination of NMR titration experiments, X-ray crystallography, and computational analysis, we analyze the effects of fluorination, substituents, ring size, and solvation on the arene-perfluoroarene interaction. We find that fluorination, extension of the π systems, and enhancement of solvent polarity greatly stabilize the stacking energy up to 3 orders of magnitude ( K a = <1 to 6000 M -1 ), with the highest K a achieved for the interaction of water-soluble variants of perfluoronaphthalene and anthracene in buffered D 2 O (pD = 12). Combining computational and experimental results, we conclude that this impressive binding energy is a result of enthalpically favorable electrostatic and dispersion interactions as well as the entropically driven hydrophobic effect. The enhanced understanding of arene-perfluoroarene interactions in aqueous solution sets the stage for the implementation of this abiotic intermolecular interaction in biology and medicine.