Anion-Manipulated Hydrolysis Process Assembles of Giant High-Nucleation Lanthanide-Oxo Cluster.

Widespread concern has been raised over the synthesis of highly nucleated lanthanide clusters with special shapes and/or specific linkages. Construction of lanthanide clusters with specific shapes and/or linkages can be achieved by carefully regulating the hydrolysis of lanthanide metal ions and the resulting hydrolysis products. However, studies on the manipulation of lanthanide-ion hydrolysis to obtain giant lanthanide-oxo clusters have been few. In this study, we obtained a tetraicosa lanthanide cluster ( 3 ) by manipulating the hydrolysis of Dy(III) ions using an anion (OAc - ). As far as we know, cluster 3 has the highest nucleation among all lanthanide-oxo clusters reported. In 3 , two triangular Dy 3 O 4 are oriented in opposite directions to form the central connecting axis Dy 6 (OH) 8 , which is in turn connected to six Dy 3 O 4 that are oriented in different directions. Meanwhile, a sample of a chiral trinuclear dysprosium cluster ( 1 ) was obtained in a mixed CH 3 OH and CH 3 CN solvent and by replacing the anion in the reaction to Cl - ions. In this cluster, 1,3,4-thiadiazole-2,5-diamine (L 2 ) is free on one side through π···π interactions and is parallel to the o -vanillin (L 1 ) - ligand, thus resulting in a triangular arrangement. The arrangement of L 2 affects the end group coordination in the cluster 1 structure through hydrogen bonding and induces the cluster to exhibit chirality. When the reaction solvent was changed to CH 3 OH, a sample of cluster 2 , composed of two independent triangular Dy 3 that have different end group arrangements, was obtained. Magnetic analysis showed that clusters 1 and 3 both exhibit distinctive single-molecule magnetic properties under zero-magnetic-field conditions. This study thus provides a method for the creation of chiral high-nucleation clusters from achiral ligands and potentially paves the way for the synthesis of high-nucleation lanthanide clusters with unique forms.