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External and internal guest binding of a highly charged supramolecular host in water: deconvoluting the very different thermodynamics.

Authors
Type
Published Article
Journal
Journal of the American Chemical Society
1520-5126
Publisher
American Chemical Society
Publication Date
Volume
132
Issue
3
Pages
1005–1009
Identifiers
DOI: 10.1021/ja9056739
PMID: 20043697
Source
Medline
License
Unknown

Abstract

NMR, UV-vis, and isothermal titration calorimetry (ITC) measurements probe different aspects of competing host-guest equilibria as simple alkylammonium guest molecules interact with both the exterior (ion-association) and interior (encapsulation) of the [Ga(4)L(6)](12-) supramolecular assembly in water. Data obtained by each independent technique measure different components of the host-guest equilibria and only when analyzed together does a complete picture of the solution thermodynamics emerge. Striking differences between the internal and external guest binding are found. External binding is enthalpy driven and mainly due to attractive interactions between the guests and the exterior surface of the assembly while encapsulation is entropy driven as a result of desolvation and release of solvent molecules from the host cavity.

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