A series of polynuclear lanthanide (Ln) complexes were prepared by the hydrolysis of the lanthanide ions using L-histidine as supporting ligand. Halide ions (X- = Cl-, Br-, and I-) have...

The rational synthesis … …ofhigh-nuclearity lanthanide clusters remains challenging.Intheir Research Article (e202205385), Min Feng, Zhiping Zheng,and co-workers developed astepwise synthesis of ahigh-nuclearity sodalite cage-like cluster Er 60 ,guided by judiciously selected anions. Thesuccessive introduction of I À ,CO 3 2À ,and NO 3 À led to the isolation of three crucial intermediate clusters,n amely the wheel-like Er 12 ,s hip-like Er 34 ,a nd bowl-like Er 48 . These findings opened the "black box" of the elusive self-assembly process and provided mechanistic insights.

The ability to construct complex molecular architectures with precise control is critical for realizing molecule‐based materials and functions. Using the assembly of a 60‐metal complex of ErIII with histidine as an example, we demonstrate the rational assembly of otherwise synthetically elusive polynuclear lanthanide hydroxide clusters directed by the combined set of I− and CO32− as templates. We succeeded in the stepwise transformation starting from Er12 to Er60 by way of two key intermediates Er34 and Er48. The Er12, Er34, and Er48 core motifs represent respectively 1/6, 1/2, and 3/4 of the complete sodalite cage of Er60. This work, representing a rare example of rationally constructing high‐nuclearity lanthanide clusters guided by judiciously chosen templates, is expected to stimulate more future efforts for the controllable synthesis of complex molecular or supramolecular architectures with unprecedented structural sophistication and possibly useful properties.

Lanthanide-oxo/hydroxo clusters (LOCs) in this mini-review refer to polynuclear complexes featuring a polyhedral metal-oxo/hydroxo cluster core of lanthanide ions exclusively or with coexisting 3d metal ions. We summarize herein the recent works using this unique family of cluster complexes for catalysis; this aspect of research stands in stark contrast to their extensively studied synthetic and structural chemistry as well as the much-researched magnetic properties. Following a brief introduction of the synthetic strategies for these clusters, pertinent results from available literature reports are surveyed and discussed according to the types of catalyzed reactions. Particular attention was paid to the selection of a cluster catalyst for a specific type of reactions as well as the corresponding reaction mechanism. To the end, the advantages and challenges in utilizing LOCs as multifunctional catalysts are summarized, and possible future research directions are proposed.