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An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
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The Lanthanide Contraction Is a Variable.

Roger E Cramer1, Jessica M Rimsza2, Timothy J Boyle3

  • 1Department of Chemistry, University of Hawaii─Manoa, 2545 McCarthy Mall, Honolulu, Hawaii 96822-2275, United States.

Inorganic Chemistry
|April 13, 2022
PubMed
Summary
This summary is machine-generated.

Lanthanide (Ln) contraction varies significantly with ligand type. Ion-dipole bonded ligands like tetrahydrofuran (THF) show enhanced Ln-contraction compared to ion-ion bonded ligands such as tris(trimethylsilyl)siloxide (SST).

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Area of Science:

  • Inorganic Chemistry
  • Lanthanide Chemistry
  • Coordination Chemistry

Background:

  • Lanthanide contraction is a well-established phenomenon in inorganic chemistry.
  • The extent of lanthanide contraction can be influenced by the coordination environment and ligand properties.
  • Previous studies have not fully elucidated the varying degrees of lanthanide contraction across different ligand types.

Purpose of the Study:

  • To investigate the variability of lanthanide (Ln) contraction in [Ln(SST)3(THF)2] and related complexes.
  • To compare the Ln-contraction behavior with different ligand types, including tris(trimethylsilyl)siloxide (SST) and tetrahydrofuran (THF).
  • To understand the underlying electronic and bonding factors contributing to the observed differences in Ln-contraction.

Main Methods:

  • Analysis of crystallographic data for lanthanide complexes from the Cambridge Structural Database (CSD).
  • Comparison of bond distances (Ln-O(THF) and Ln-O(SST)) across the lanthanide series (La to Lu).
  • Gas-phase electronic structure calculations using density functional theory (DFT).

Main Results:

  • A significantly larger variation in Ln-O(THF) bond distances (0.257 Å) compared to Ln-O(SST) (0.164 Å) was observed across the lanthanide series.
  • This enhanced Ln-contraction for THF was found to be pervasive across similar structures and also observed with pyridine ligands.
  • DFT calculations confirmed the experimental findings, attributing the variable Ln-contraction to differences in bonding types: ion-ion for Ln-SST and ion-dipole for Ln-THF.

Conclusions:

  • The type of bonding interaction between the lanthanide ion and the ligand is a critical factor determining the extent of lanthanide contraction.
  • Ion-dipole interactions (e.g., with THF) lead to a more pronounced lanthanide contraction compared to ion-ion interactions (e.g., with SST).
  • This study provides a deeper understanding of the factors governing lanthanide contraction, essential for predicting and designing lanthanide-based materials.