NDLI: Water <i>vs.</i> cucurbituril rim: a fierce competition for guest solvation

Content Provider	Royal Society of Chemistry (RSC)
Author	Francescon, John Masson, Eric Ling, Xiaoxi Xiao, Lifeng Saretz, Stefan
Copyright Year	2016
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.
Starting Page	3569
Ending Page	3573
Page Count	5
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	7
Issue Number	6
Journal	Chemical Science
DOI	10.1039/c5sc04475h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Ammonium Cucurbitaceae Swain Substituent Molecular geometry Macrocycle Solvation Linear combination Homologous series Lupton Resonance Electrostatics CB
Content Type	Text
Resource Type	Article
Subject	Chemistry

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