A series of polyoxometalate-based cyclophanes (polyoxometalatocyclophanes) were synthesized via covalent linkage of Lindqvist-type hexamolybdate clusters with bis-arylimido ligands bearing flexible alkyl chains. Single-crystal X-ray diffraction and circular dichroism spectroscopy confirm that compound 3, ((n-C₄H₉)N)₂[Mo₆O₁₇N(o-phenyl-O(CH₂)₅O-phenyl-o)N], undergoes spontaneous chiral resolution upon crystallization. Biological evaluation against the leukemia K562 cell line shows that, among the tested compounds, including aromatic amine ligands, hexamolybdate salts, and related polyoxometalatocyclophanes, compound 3 exhibits the highest inhibitory activity. At higher concentrations, its activity surpasses that of the positive control, 5-fluorouracil (5-FU). Molecular docking and molecular dynamics simulations indicate that the [Mo₆O₁₇N(o-phenyl-O(CH₂)₅O-phenyl-o)N]²⁻ anion adopts a compact conformation and can effectively bind to the anti-apoptotic protein Bcl-2, with a predicted binding affinity of −27.39 kcal/mol.

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.