Ion-Selective Assembly of Supertetrahedral Selenido Germanate Clusters for Alkali Metal Ion Capture and Separation

[Image: see text] Supertetrahedral chalcogenido (semi)metalate cluster-based frameworks possess high selectivity for alkali metal cations, matching the specific charge density of their inner surfaces, which enables their use as ion-exchange materials. Aggregates of the supertetrahedral chalcogenido metalate cluster offer even new perspectives for metal ion capture and separation. Herein, we report on ionothermal preparation of two corresponding model compounds, (C(2)C(1)Im)(7)[Cs@Ge(II)(4)(Ge(IV)(4)Se(10))(4)] (1) and (C(2)C(1)Im)(10)[Na(5)(CN)(6)@Cu(6)(Ge(4)Se(10))(4)(Cu)] (2). Their formation is reliant on one specific cation type each, Cs(+) for 1 and Na(+) for 2, thus providing promising separation potential during crystallization. Compound 1 is based on the largest discrete binary selenido germanate cluster reported to date and the first mixed-valent chalcogenido germanate(II/IV) supertetrahedron. Moreover, it adds to the few examples of chalcogenides capable of capturing Cs(+) ions. Its high selectivity for Cs(+) compared to that of Li(+), Na(+), K(+), and Rb(+) was confirmed by single-crystal X-ray diffraction, energy-dispersive X-ray spectroscopy, and electrospray ionization mass spectrometry. Quantum chemical studies indicate that smaller ions, K(+) and Rb(+), could also be embedded in an isolated cluster assembly, but as the cluster aggregate slightly distorts for crystallization, the selectivity for Cs(+) becomes exclusive in the salt. The anionic substructure of compound 2 is based on a two-dimensional network of supramolecular assemblies and exhibits an exclusive preference for Na(+). This work thus provides the first comprehensive insight into the selective incorporation of specific alkali metal ions into supramolecular aggregates of supertetrahedral chalcogenide clusters, as a promising basis for new ion trapping techniques—especially for heavy alkali metal ions that pose environmental challenges.