RESUMEN
We describe a study of the influence of cryptand denticity on the structural, electronic, and electrochemical properties of UIII-containing cryptates. Two cryptands (2.2.2 and 2.2.1) are reported. The cryptand with the smaller denticity leads to negative electrochemical potentials and shorter bond lengths that are consistent with a better fit for UIII than the larger cryptand. These studies provide insight into the rational design of cryptand-based ligands for trivalent uranium.
RESUMEN
Low-valent f-block metals have intrinsic luminescence, electrochemical, and magnetic properties that are modulated with ligands, causing the coordination chemistry of these metals to be imperative to generating critical insights needed to impact modern applications. To this end, we synthesized and characterized a series of twenty-seven complexes of f-metal ions including EuII, YbII, SmII, and UIII and hexanuclear clusters of LaIII and CeIII to study the impact of tris[2-(2-methoxyethoxy)ethyl]amine, a flexible acyclic analogue of the extensively studied 2.2.2-cryptand, on the coordination chemistry and photophysical properties of low-valent f-block metals. We demonstrate that the flexibility of the ligand enables luminescence tunability over a greater range than analogous cryptates of EuII in solution. Furthermore, the ligand also displays a variety of binding modes to f-block metals in the solid state that are inaccessible to cryptates of low-valent f-block metals. In addition to serving as a ligand for f-block metals of various sizes and oxidation states, tris[2-(2-methoxyethoxy)ethyl]amine also deprotonates water molecules coordinated to trivalent triflate salts of f-block metal ions, enabling the isolation of hexanuclear clusters containing either LaIII or CeIII. The ligand was also found to bind more tightly to YbII and UIII in the solid state compared to 2.2.2-cryptand, suggesting that it can play a role in the isolation of other low-valent f-block metals such CfII, NpIII, and PuIII. We expect that our findings will inspire applications of tris[2-(2-methoxyethoxy)ethyl]amine in the design of light-emitting diodes and the synthesis of extremely reducing divalent f-block metal complexes that are of interest for a wide range of applications.
RESUMEN
With the great demand for europium in green-energy technologies comes the need for innovative methods to isolate the elements. We introduce a solid-liquid extraction method using a 2.2.2-cryptand-modified solid support to separate europium from gadolinium using their differences in electrochemical potential. The method overcomes challenges associated with the separation of those two ions that have similar coordination chemistry in the +3 oxidation state. A competitive adsorption study in the cryptand system between EuII/EuIII and GdIII shows greater affinity for EuII relative to GdIII. After separation from GdIII, Eu was released by oxidizing EuII to EuIII with 99.3% purity. The purity of separated Eu is unaffected by pH between pH 3.0 and 5.5. Overall, we demonstrate that by modifying a solid support with 2.2.2-cryptand, divalent europium can be separated from trivalent gadolinium based on the differences of affinities of 2.2.2-cryptand for the two ions.
