Modulating the Supramolecular Assembly of <i>α</i>‐Cyclodextrin and Anderson‐type Polyoxometalate through Covalent Modifications

A series of unprecedented supramolecular complexes of covalently modified Anderson-type polyoxometalates (POMs) and α-cyclodextrins (α-CDs) have been obtained and characterized in solid state by single-crystal X-ray diffraction, and in aqueous solution using various techniques including ¹H DOSY NMR, 2D NOESY ¹H NMR, isothermal titration calorimetry (ITC), and electrospray ionization time-of-flight mass spectroscopy (ESI-TOF-MS). It has been demonstrated that the supramolecular assembly process could be modulated by different covalent modification modes of the Anderson POMs, giving rise to a new type of POM/α-CD complexes featuring organic-inorganic pseudo-rotaxane structures, which are in good contrast to those of POM/γ-CD complexes of poly-rotaxane structures. Moreover, it is delighted to find that these pseudo-rotaxanes of POM/α-CD complexes exhibit stable chirality in aqueous solution, which has not been accomplished in previously reported POM/CD assemblies.