Water vs cucurbituril rim: a fierce competition for guest solvation

Chemical Science
Xiaoxi LingEric Masson

Abstract

The impact of remote substituents on the affinity of cucurbit[n]urils (CB[n]) towards a homologous series of guests, which differ from one another only by a single substituent, and adopt the same geometry within the cavity of the macrocycle, is presented for the first time, and is used to decipher the competition between water and the carbonylated portal of CB[7] for the stabilization of positively charged guests. Binding affinities of CB[7] towards substituted N-benzyl-trimethylsilylmethylammonium cations relative to the unsubstituted member (X = H) range from 0.9 (X = CH3) to 3.1 (X = SO2CF3), and correlate very precisely with a linear combination of Swain-Lupton field/inductive (F; 67%) and resonance (R; 33%) parameters tabulated for each substituent. We show that this subtle sensitivity results exclusively from the balance between two competing mechanisms, on which the substituents exert an approximately 11 times greater impact: (1) the solvation of the ammonium unit and its immediate surroundings by water in the free guests, and (2) the coulombic attraction between the ammonium unit and the rim of CB[7] in the complexes.

References

Feb 14, 2004·The Journal of Organic Chemistry·Winston Ong, Angel E Kaifer
Jul 30, 2005·Angewandte Chemie·Jason LagonaLyle Isaacs
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Nov 10, 2005·Journal of the American Chemical Society·Simin LiuLyle Isaacs
Dec 21, 2007·Proceedings of the National Academy of Sciences of the United States of America·Mikhail V RekharskyYoshihisa Inoue
Dec 22, 2009·Organic & Biomolecular Chemistry·Ian W Wyman, Donal H Macartney
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Jul 12, 2012·Chemistry : a European Journal·Stefan Grimme
Aug 14, 2012·Journal of the American Chemical Society·Frank BiedermannAlfonso De Simone
Sep 3, 2013·Journal of the American Chemical Society·Frank BiedermannWerner M Nau

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Citations

Aug 6, 2016·Chemistry : a European Journal·Nengfang SheLyle Isaacs
Mar 31, 2018·Chemistry : a European Journal·Kondalarao Kotturi, Eric Masson
Mar 10, 2018·Chemistry, an Asian Journal·Katsuhiko ArigaWaka Nakanishi
Feb 15, 2017·Chemistry : a European Journal·Emanuela CavatortaJurriaan Huskens
Feb 15, 2018·Journal of the American Chemical Society·Mersad RaeisiEric Masson
Sep 28, 2016·Journal of the American Chemical Society·Alexandra I LazarWerner M Nau
Dec 7, 2018·Chemical Reviews·Teresa L MakoMindy Levine
Feb 10, 2017·Journal of the American Chemical Society·David SigwaltLyle Isaacs
May 24, 2017·Journal of the American Chemical Society·Ofer ReanyEhud Keinan

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Methods Mentioned

BETA
nuclear magnetic resonance
isothermal titration calorimetry
NMR

Software Mentioned

IEFPCM
COSMO

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