Macromolecular Recognition of Cyclodextrin: Inversion of Selectivity of β‐Cyclodextrin toward Adamantyl Groups Induced by Macromolecular Chains

Interaction of β-cyclodextrin (β-CD) with alternating copolymers (pAdMA and pAdPhMA) of sodium maleate with adamantyl (Ad) and with adamantylphenyl (AdPh) vinyl ether has been investigated by several NMR techniques. Comparing the apparent association constants (K) for the polymers with the K for the model compounds, which are determined by the analysis of (1) H NMR and isothermal titration calorimetry data, respectively, the selectivities of β-CD toward Ad and AdPh moieties are contrasting for the model and polymer systems. This phenomenon is described by circular dichroism and 2D NMR as follows; the most stable inclusion complex for the β-CD/AdPh model system is extremely destabilized for the corresponding polymer system because of competition with hydrophobic interaction between neighboring AdPh moieties.