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Updated: Aug 18, 2026

Modification and Functionalization of the Guanidine Group by Tailor-made Precursors
Published on: April 27, 2017
Probing binding-mode diversity in guanidinium-oxoanion host-guest systems
Manal Haj-Zaroubi1, Franz P Schmidtchen
1Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, 85747 Garching, Germany.
Abstract:
An attempt to experimentally estimate the role of binding-mode diversity (structural fuzziness) on the molecular recognition seen in the prominent guanidinium-oxoanion host-guest pair is described. The global heat response as measured by isothermal titration calorimetry in acetonitrile, which was obtained from the interaction of five different but structurally closely related guanidinium hosts with three rigid phosphinate guests of decreasing accessibility of their binding sites, is correlated to provide a trend analysis. All host-guest associations of 1:1 stoichiometry in this series are strongly enthalpy-driven. The change in complexation entropy can be related to the tightness of the mutual fit of the host-guest partners, which approaches a minimum limit and is interpreted as the unique lock-and-key binding mode. The ordinary host-guest complexation in this ensemble features substantial positive entropy changes that correlate inversely with the binding interface area. This finding excludes desolvation effects as the major cause of entropy production, and provides evidence for the existence of a broad variety of complex configurations rather than a single binding mode to represent the associated host-guest pair. This result bears on the molecular design of systems that vitally depend on structural fidelity, such as nanoassemblies or homogeneous catalysis.
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