Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Materials Science

Background:

• Low coordinate metal complexes offer unique properties but are challenging for lanthanides (Ln) due to their ionic bonding preferences.
• Lanthanide(II) complexes with two ligands exist, but lanthanide(III) analogues are rare due to stronger electrostatic interactions.

Purpose of the Study:

• To synthesize and characterize low-coordinate lanthanide(III) complexes.
• To investigate the impact of ligand environment on the electronic and magnetic properties of lanthanide(III) ions.

Main Methods:

• Synthesis of lanthanide(III) complexes featuring two bis(silyl)amide ligands.
• Solid-state characterization of the ytterbium(III) analogue using techniques like X-ray crystallography.
• Analysis of crystal field environments and comparison with theoretical predictions.

Main Results:

• Successful synthesis of bent lanthanide(III) complexes with two bis(silyl)amide ligands.
• The ytterbium(III) complex exhibited a crystal field in the solid state that deviated from axial predictions, resembling a three-coordinate precursor.
• Observed geometry significantly influenced the magnetic ground state, overriding the expected effect of lanthanide ion identity.

Conclusions:

• Geometry plays a critical role in determining the magnetic properties of low-coordinate lanthanide complexes.
• Findings challenge established electronic structure models for two-coordinate lanthanide systems.
• Provides essential insights for designing lanthanide-based materials with tailored magnetic characteristics.