Lanthanide clusters with azide capping ligands.

Area of Science:

• Inorganic Chemistry
• Materials Science
• Lanthanide Chemistry

Background:

• Azide ligands serve as effective surface caps in synthesizing lanthanide oxo and selenido clusters.
• Lanthanide complexes are crucial in various fields, including catalysis and materials science.

Purpose of the Study:

• To synthesize novel lanthanide oxo and selenido clusters using azide ligands.
• To characterize the structure and properties of these newly formed clusters.

Main Methods:

• Synthesis of lanthanide clusters via addition of sodium azide (NaN3) and sodium oxide (Na2O) to lanthanide tris(phenylselenide) [Ln(SePh)3] solutions in pyridine.
• Characterization using low-temperature single-crystal X-ray diffraction.
• Preparation of chalcogenido derivatives through ligand-based redox reactions with elemental selenium.

Main Results:

• Formation of (py)18Sm6Na2O2(N3)16 and (py)10Ln6O2(N3)12(SePh)2 (Ln = Ho, Er) clusters.
• Successful synthesis of a diselenido cluster, (py)10Er6O2(SeSe)2(N3)10, exhibiting crystallographic disorder.
• All synthesized lanthanide clusters were found to detonate upon heating.

Conclusions:

• Azide ligands are versatile for constructing complex lanthanide oxo and selenido cluster architectures.
• The characterized clusters represent new additions to the family of lanthanide coordination compounds.
• The inherent instability (explosive nature) of these clusters is a critical safety consideration.