Anion-Guided Stepwise Assembly of High-Nuclearity Lanthanide Hydroxide Clusters

Area of Science:

• Coordination Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Precise control over molecular architecture is crucial for developing molecule-based materials.
• Synthesizing complex, high-nuclearity lanthanide clusters remains a significant challenge in chemistry.

Purpose of the Study:

• To demonstrate the rational assembly of elusive polynuclear lanthanide hydroxide clusters.
• To achieve controllable synthesis of complex molecular architectures with high structural sophistication.

Main Methods:

• Utilized a combined template set of iodide (I^-) and carbonate (CO₃^2-) ions.
• Employed stepwise synthesis, starting from Er₁₂ to Er₆₀, with intermediates Er₃₄ and Er₄₈.
• Focused on the assembly of erbium (Er^III) complexes with histidine.

Main Results:

• Successfully demonstrated the rational assembly of Er₆₀ hydroxide clusters.
• Achieved stepwise transformation from Er₁₂ to Er₆₀ via Er₃₄ and Er₄₈ intermediates.
• Identified core motifs of Er₁₂, Er₃₄, and Er₄₈ as fractions of the final sodalite cage structure.

Conclusions:

• This work presents a rare example of rationally constructing high-nuclearity lanthanide clusters using templates.
• The findings are expected to inspire future research in the controllable synthesis of complex molecular and supramolecular architectures.
• The developed methodology could lead to materials with novel properties due to enhanced structural sophistication.