Controlling the Assembly of Chalcogenide Anions in Ionic Liquids: From Binary Ge/Se through Ternary Ge/Sn/Se to Binary Sn/Se Frameworks

Seven compounds with binary or ternary Ge/Se, Ge/Sn/Se, or Sn/Se anionic substructures crystallized upon the ionothermal reactions of K₄(H₂O)₃]Ge₄Se₁₀] with SnCl₄ ? 5 H₂O or SnCl₂ in BMMIm]BF₄] or BMIm]BF₄] (BMMIm=1‐butyl‐2,3‐dimethyl‐imidazolium, BMIm=1‐butyl‐3‐methyl‐imidazolium). The products were obtained by subtly varying the reaction conditions; the nature and amount of an additional amine was the most important parameter in the product selection and in determining the Sn/Ge ratio in the isolated products. The crystal structures of these chalcogenides were based on complex anions with unprecedented topologies that varied from discrete clusters (0D) through 1D chain structures or 2D layers to 3D frameworks. The architecture and composition of the title compounds were well reflected by their optical absorption behavior. Herein, we report a convenient approach for the generation of chalcogenidometallate phases with fine‐tunable electronic properties in ionic liquids, which have been inaccessible by traditional methods.