Solvent attenuation of dispersion interactions quantified in polar and nonpolar media using rigid CH–π balances

Solvent attenuation of dispersion interactions was quantified using a new class of rigid intramolecular CH-π molecular balances. These balances incorporate small, two-carbon CH donors that minimize solvophobic effects and isolate the dispersion component. Folding energies (Δ<i>G</i> <sub>exp</sub>) were measured across eight solvents: cyclohexane, toluene, chloroform, ethyl acetate, acetone, acetonitrile, DMSO, and methanol. Attenuation values in nonpolar solvents closely matched those reported by Peter Chen using a bimolecular host-guest system. Our use of a molecular balance also enabled study in polar solvents where the attenuation remained similarly high in polar solvents such as DMSO and methanol. The narrow 75 to 80 percent range observed across all solvents demonstrates the consistency of dispersion attenuation and the effectiveness of molecular balances in quantifying weak noncovalent forces while avoiding interference from solvent driven effects. Comparisons between sp<sup>2</sup> and sp<sup>3</sup> CH donors showed similar dispersion contributions, with sp<sup>2</sup> groups exhibiting stronger overall interactions due to greater electrostatic stabilization. As a result, sp<sup>2</sup> CH groups formed stronger interactions in nonpolar solvents, while both CH types showed similar strengths in polar solvents.

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Publication Details

Journal
Chemical Science
Published
2025-01-01
DOI
https://doi.org/10.1039/d5sc02852c
Citations
1
Primary Topic
Spectroscopy and Quantum Chemical Studies
Type
article
Field-Weighted Citation Impact
1.25

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article

Solvent attenuation of dispersion interactions quantified in polar and nonpolar media using rigid CH–π balances

Mark D. Smith, Ken D. Shimizu, Binzhou Lin, Hao Liu et al.
1 citations
Chemical Science
Spectroscopy and Quantum Chemical Studies
1.25
article

Solvent attenuation of dispersion interactions quantified in polar and nonpolar media using rigid CH–π balances

Mark D. Smith, Ken D. Shimizu, Binzhou Lin, Hao Liu, Xiaolong Huang, Harrison M. Scott
article en
1 citations

Abstract

Solvent attenuation of dispersion interactions was quantified using a new class of rigid intramolecular CH-π molecular balances. These balances incorporate small, two-carbon CH donors that minimize solvophobic effects and isolate the dispersion component. Folding energies (Δ<i>G</i> <sub>exp</sub>) were measured across eight solvents: cyclohexane, toluene, chloroform, ethyl acetate, acetone, acetonitrile, DMSO, and methanol. Attenuation values in nonpolar solvents closely matched those reported by Peter Chen using a bimolecular host-guest system. Our use of a molecular balance also enabled study in polar solvents where the attenuation remained similarly high in polar solvents such as DMSO and methanol. The narrow 75 to 80 percent range observed across all solvents demonstrates the consistency of dispersion attenuation and the effectiveness of molecular balances in quantifying weak noncovalent forces while avoiding interference from solvent driven effects. Comparisons between sp<sup>2</sup> and sp<sup>3</sup> CH donors showed similar dispersion contributions, with sp<sup>2</sup> groups exhibiting stronger overall interactions due to greater electrostatic stabilization. As a result, sp<sup>2</sup> CH groups formed stronger interactions in nonpolar solvents, while both CH types showed similar strengths in polar solvents.

Chemical ScienceVol. 16(38)
University of South Carolina (US)
National Science Foundation, Division of Chemistry
Openalex Percentile: Top 18%
Spectroscopy and Quantum Chemical Studies
1.25
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Solvent attenuation of dispersion interactions quantified in polar and nonpolar media using rigid CH–π balances — Mark D. Smith, Ken D. Shimizu, et al. · Chemical Science (2025) | TGRS Research Map | TGRS