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

Abstract

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, 1,3,4thiadiazole-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.

Highly stable drone-shaped lanthanide clusters: structure, assembly mechanism, and crystalline–amorphous transitions

“…These findings showed that this temperature-decreasing χ m T value may be due to the decrease in the Stark sublevel of the Dy( iii ) excited state and the induced crystal-field effect. 33 Furthermore, the field-dependent magnetization of cluster 1 was tested at different temperatures (2–5 K) and applied fields of 0–7 T, and the M vs. H / T curves were plotted (Fig. 5b).…”

“…26 Our research group has also made some progress in exploring the formation of high-nuclear lanthanide clusters. [29][30][31][32][33][34] For example, in 2019, we obtained Dy 10 nanoclusters with multiple relaxation behaviors by using Schiff base organic ligands having multidentate chelation coordination sites. After exploring their formation process, a step-bystep assembly mechanism was proposed by HRESI-MS. 29 We then constructed a cage-shaped cluster Dy 14 by connecting disc-shaped lanthanide clusters with strong hydrogen bonds and proposed its assembly mechanism.…”

Visual and Real-Time Monitoring of Cd2+ in Water, Rice, and Rice Soil with Test Paper Based on [2 + 2] Lanthanide Clusters

“…Bond angles and bond lengths for Tb 2 Tb 2 are within the normal range of lanthanide clusters (Tables S1 and S2). − …”

Composition Control in Molecular Cluster-Aggregates: A Toolbox for Optical Output Tunability via Energy Transfer Pathways

“…From this perspective, Ln III -based molecular cluster-aggregates (MCAs) have emerged as a suitable platform for luminescence at the nanoscale. − In addition to a large number of emitting centers within a precise crystalline structure, MCAs offer excellent control over uniformity and composition. − On top of that, the careful choice of a ligand moiety ensures, at the same time, core rigidity (which reduces phonon-assisted deactivation routes) and a suitable way to efficiently sensitize Ln III optical centers. The so-called “antenna effect” is essential to account for the low absorption coefficient of Ln III and accomplish high performance.…”