Journal article

Publication year: 2021

Pages: 41-45

Journal: Journal of the American Chemical Society

Volume number: 143

Issue number: 1

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/jacs.0c09597

Publisher: American Chemical Society

Abstract: 

We present a comprehensive experimental study of a di-t-butyl-substituted cyclooctatetraene-based molecular balance to measure the effect of 16 different solvents on the equilibrium of folded versus unfolded isomers. In the folded 1,6-isomer, the two t-butyl groups are in close proximity (H···H distance ≈ 2.5 Å), but they are far apart in the unfolded 1,4-isomer (H···H distance ≈ 7 Å). We determined the relative strengths of these noncovalent intramolecular σ-σ interactions via temperature-dependent nuclear magnetic resonance measurements. The origins of the interactions were elucidated with energy decomposition analysis at the density functional and ab initio levels of theory, pinpointing the predominance of London dispersion interactions enthalpically favoring the folded state in any solvent measured.

Harvard Citation style: Schümann, J., Wagner, J., Eckhardt, A., Quanz, H. and Schreiner, P. (2021) Intramolecular London Dispersion Interactions Do Not Cancel in Solution, Journal of the American Chemical Society, 143(1), pp. 41-45. https://doi.org/10.1021/jacs.0c09597

APA Citation style: Schümann, J., Wagner, J., Eckhardt, A., Quanz, H., & Schreiner, P. (2021). Intramolecular London Dispersion Interactions Do Not Cancel in Solution. Journal of the American Chemical Society. 143(1), 41-45. https://doi.org/10.1021/jacs.0c09597