Lanthanides Singing the Blues: Their Fascinating Role in the Assembly of Gigantic Molybdenum Blue Wheels

[Image: see text] Molybdenum blues (MBs) are a distinct class of polyoxometalates, exhibiting versatile/impressive architectures and high structural flexibility. In acidified and reduced aqueous environments, isopolymolybdates generate precisely organizable building blocks, which enable unique nanoscopic molecular systems (MBs) to be constructed and further fine-tuned by hetero elements such as lanthanide (Ln) ions. This Review discusses wheel-shaped MB-based structure types with strong emphasis on the ∼30 Ln-containing MBs as of August 2021, which include both organically hybridized and nonhybridized structures synthesized to date. The spotlight is thereby put on the lanthanide ions and ligand types, which are crucial for the resulting Ln-patterns and alterations in the gigantic structures. Several critical steps and reaction conditions in their synthesis are highlighted, as well as appropriate methods to investigate them both in solid state and in solution. The final section addresses the homogeneous/heterogeneous catalytic, molecular recognition and separation properties of wheel-shaped Ln-MBs, emphasizing their inimitable behavior and encouraging their application in these areas.