Self‐Assembly of Hexanuclear Lanthanide Carboxylate Clusters of Three Architectures

Synthesis of new lanthanide‐based poly‐hydroxo clusters is a key challenge in the deliberate design of novel metal‐organic frameworks with functional properties. Most of the current approaches fail to isolate stable hexanuclear entities to be used as pre‐existing building blocks for such frameworks. Herein we highlight the new two‐step synthetic route for the new family of hexanuclear lanthanide hydroxo pivalate compounds: self‐controlled hydrolysis and subsequent introduction of amine ligand. Three different octahedral architectures stabilized by intermolecular hydrophobic interactions and intramolecular H‐bonds have been found within the system of lanthanide pivalate and diethylenetriamine, and supramolecular organization of the compounds was examined. This is the first demonstration of isolation of hollow and O‐centered Ln III 6 (OH) 8 cluster from the same system.