Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures.

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.

Solid-state and solution-phase characterization of SmII-aza[2.2.2]cryptate and its methylated analogue.

Two new SmII-azacryptates are reported that differ in steric hindrance and Lewis basicity of donor atoms. The sterically hindered complex has a smaller coordination number and a more negative electrochemical potential than the complex with less steric hindrance.