Three Giant Lanthanide Clusters Ln₃₇ (Ln = Gd, Tb, and Eu) Featuring A Double-Cage Structure

Area of Science:

• Inorganic Chemistry
• Materials Science
• Magnetochemistry

Background:

• High-nuclearity lanthanide clusters are of interest for their unique structures and magnetic properties.
• Lanthanide complexes can exhibit single-molecule magnet behavior and potential applications in cooling technologies.

Purpose of the Study:

• To synthesize and characterize novel homometallic high-nuclearity lanthanide clusters.
• To investigate the structural and magnetic properties of these clusters, particularly their potential for magnetic cooling.

Main Methods:

• Solvothermal synthesis involving lanthanide perchlorates, acetate ligands, and 1,2,3-cyclohexanetriol.
• Single-crystal X-ray diffraction for structural determination.
• Magnetic susceptibility measurements to determine magnetic entropy change.

Main Results:

• Three homometallic clusters, Ln₃₇ (Ln = Gd, Tb, Eu), with double cage-like structures were successfully synthesized.
• The largest cluster, Gd₃₇, displayed a significant magnetic entropy change of 38.7 J kg^-1 K^-1.
• The structures incorporate carbonate, acetate, hydroxide, and water ligands, with extensive solvent molecules.

Conclusions:

• The successful synthesis of Ln₃₇ clusters expands the library of high-nuclearity lanthanide compounds.
• The observed magnetic entropy change in Gd₃₇ highlights its potential as a cooling agent in magnetic refrigeration.
• The double cage structure offers a novel platform for exploring lanthanide cluster chemistry and applications.