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

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 similar to 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.

Automated summary

This review discusses the classification, structural characteristics, and interactions with lanthanide ions of molybdenum blues. The focus is on wheel-shaped structures of molybdenum blues, including both organic and inorganic hybrid structures, and highlights the key factors and research methods in their synthesis. The unique behavior and potential applications of wheel-shaped Ln-MBs in catalysis, molecular recognition, and separation are emphasized.