Nonconventional Three-Component Hierarchical Host-Guest Assembly Based on Mo-Blue Ring-Shaped Giant Anion, γ-Cyclodextrin, and Dawson-type Polyoxometalate.

In this communication, we report on a noteworthy hybrid supramolecular assembly built from three functional components hierarchically organized through noncovalent interactions. The one-pot synthesis procedure leads to the formation of large Mo-blue ring-shaped anion {Mo ₁₅₄ }, which contains the supramolecular adduct based on the symmetric encapsulation of the Dawson-type [P ₂ W ₁₈ O ₆₂ ] ^6- anion by two γ-cyclodextrin units. Such a nanoscopic onion-like structure, noted [P ₂ W ₁₈ O ₆₂ ]@2γ-CD@{Mo ₁₅₄ } has been characterized by single-crystal X-ray diffraction, thus demonstrating the capability of the giant inorganic torus to develop relevant supramolecular chemistry, probing the strong affinity of the inner and outer faces of the γ-CD for the polyoxometalate surfaces. Furthermore, interactions and behavior in solution have been studied by multinuclear NMR spectroscopy, which supports specific interactions between γ-CD and POM units. Finally, the formation of this three-component hybrid assembly from one-pot procedure, in water and using nearly stoichiometric conditions, is discussed in terms of the driving forces orchestrating this highly efficient multilevel recognition process.