Using chain-like polyethers consisting of two terminal –NH₂ groups and (TBA)₄[α-Mo₈O₂₆] as starting materials, two polyoxometalatocrown ethers were prepared by a cyclization reaction through the formation of Mo≡N triple bonds: (TBA)₂[Mo₆O₁₇N(o-C₆H₄OCH₂(CH₂OCH₂)_nCH₂OC₆H₄-o)N] (compounds 1, n = 1; 2, n = 2). As confirmed by single-crystal X-ray diffraction and infrared (IR) studies, the polyoxometalatocrown ether 2 can capture primary ammonium cations in solid state.

In this study, we present a comprehensive overview of supramolecular self-assemblies comprising cyclodextrins (CDs) and polyoxometalates (POMs). We summarize the recent advancements in supramolecular POM–CD systems, including their structures, functions, and applications. Subsequently, we focus on the self-assembly behavior of CDs and POMs, encompassing the formation of inclusion complexes, host–guest interactions, and the development of hybrid materials. In addition, we discuss the remarks on future outlooks and hope that this review will serve as a valuable reference for researchers engaged in the fields of supramolecular/POM chemistry, materials science, and nanotechnology.