Donor Radii in Rare-Earth Complexes

Area of Science:

• Inorganic Chemistry
• Solid-State Chemistry
• Computational Chemistry

Background:

• Rare-earth elements form diverse complexes with varying Ln-donor distances.
• Accurate prediction of these distances is crucial for understanding chemical properties.

Purpose of the Study:

• To establish a reliable set of donor radii for rare-earth cations.
• To enable accurate prediction of Ln-donor bond distances.
• To aid in the analysis of structural data and identification of bonding interactions.

Main Methods:

• Analysis of structural data from the Cambridge Structural Database (CSD).
• Theoretical calculations using density functional theory (DFT) and NEVPT2 wave function approaches.
• Linear fitting of experimental bond distances to derive donor radii (rD).

Main Results:

• Ln-donor distances correlate with cation and donor contributions.
• Derived donor radii (rD) align with Shannon's crystal radii (CR).
• Established rD values predict Ln-donor distances across different rare-earth cations and oxidation states.
• Identified potential errors in existing X-ray structural assignments.

Conclusions:

• The new donor radii provide a robust tool for predicting rare-earth cation-donor distances.
• These radii enhance the interpretation of structural data, revealing interaction strengths.
• The findings have significant implications for understanding the stability and reactivity of rare-earth metal ion complexes.