Ionic Contraction across the Lanthanide Series Decreases the Temperature-Induced Disorder of the Water Coordination...

In liquid, temperature affects the structures of lanthanide complexes in multiple ways that depend upon complex interactions between ligands, anions, and solvent molecules. The relative simplicity of lanthanide aqua ions (Ln³⁺) make them well suited to determine how temperature induces structural changes in lanthanide complexes. We performed a combination of ab initio molecular dynamics (AIMD) simulations and extended X-ray absorption fine structure (EXAFS) measurements, both at 25 and 90 °C, to determine how temperature affects the first- and second-coordination spheres of three Ln³⁺ (Ce³⁺, Sm³⁺, and Lu³⁺) aqua ions. AIMD simulations show first lanthanide coordination spheres that are similar at 25 and 90 °C, more so for the Lu³⁺ ion that remains as eight-coordinate than for the Ce³⁺ and Sm³⁺ ions that change their preferred coordination number from nine (at 25 °C) to eight (at 90 °C). The measured EXAFS spectra are very similar at 25 and 90 °C, for the Ce³⁺, Sm³⁺, and Lu³⁺ ions, suggesting that the dynamical disorder of the Ln³⁺ ions in liquid water is sufficient such that temperature-induced changes do not clearly manifest changes in the structure of the three ions. Both AIMD simulations and EXAFS measurements show very similar structures of the first coordination sphere of the Lu³⁺ ion at 25 and 90 °C.