Xiamen University Makes Progress in Rare Earth-Transition Metal Clusters

Recently, the research group of Xiamen University has made new progress in the module assembly of high nuclear rare earth-transition metal (3d-4f) clusters. The relevant study titled: “Synthetic Protocol for Assembling Giant Heterometallic Hydroxide Clusters from Building Blocks: Rational Design and Efficient Synthesis" was published in the Matter journal under Cell Publishing.

Giant heterometallic lanthanide and transition metal (3d-4f) clusters are regarded as one of the most promising multiple-functional molecule-based materials. Although the synergistic effect from multiple 3d and 4f metal ions has exhibited impressive properties in many fields, developments of giant 3d-4f clusters have been limited by their poor designability. Nanoscale molecular materials obtained from building-block methods have flourished in recent years and have stimulated further efforts to more challenging systems.

Starting from a well-designed building element, synthesizing the target product through a bottom-up assembly method is an important way to achieve directional synthesis. However, so far, people's understanding of building elements involving a large number of coordination bonds is still limited. Therefore, how to realize the modular assembly of the rare earth-transition metal cluster building element is still a major challenge.

In response to this problem, Kong Xiangjian and Long Lasheng's research team from Xiamen University proposed a new method for assembling high-nuclear 3d-4f clusters using structural elements based on their long-term experience in synthesizing high-nuclear 3d-4f clusters.

The research team selected multiple structural primitives from the crystallographic database as potential construction primitives, used high-resolution mass spectrometry to detect the formation conditions and evolution mechanisms of these structural primitives. Finally, the target structural element synthesized in situ was used as the assembly module. The two high-nuclear 3d-4f clusters Ln₇₆Ni₈₈ and Ln₆₈Ni₉₀ were successfully synthesized. Among them, Ln₇₆Ni₈₈ is the currently reported highest nuclear 3d-4f cluster.

This work of Xiamen University attempts to realize the controlled assembly of elusive 3d-4f clusters by identifying reliable building blocks from a database and understanding their growth mechanism. Based on preparing building blocks as "Lego" bricks, more giant 3d-4f cluster structures can be predicted according to topology rules. The proposed protocol is expected to be an effective method to realize the directed synthesis of giant heterometallic 3d-4f clusters. The research work of module assembly of rare earth-transition metal clusters was funded by the National Natural Science Foundation of China.

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