Ionothermal Synthesis of Tetranuclear Borate Clusters Containing f- and p‑Block Metals

The reactions of simple oxides or halides of trivalent lanthanides and actinides or bismuth with boric acid in the ionic liquid 1-butyl-3-methyl­imid­azolium chloride at 150 °C result in the formation and crystallization of a series of isomorphous tetranuclear borate clusters with the general formula M4B22O36(OH)6(H2O)13 (M = La, Ce, Pr, Nd, Sm, Eu, Gd, Pu, and Bi). These clusters do not assemble with trivalent cations smaller than Gd3+, suggesting that the formation of the clusters is dictated by the size of the metal ion. The cations are found in cavities along the periphery of a cage assembled from the corner- and edge-sharing interactions of BO3 triangles and BO4 tetrahedra, yielding a complex chiral cluster. Both enantiomers cocrystallize. The metal ions are nonacoordinate, and their geometries are best described as distorted tridiminished icosahedra. This coordination environment is new for both Pu3+ and Bi3+. In addition to detailed structural information, UV/vis–NIR absorption and photoluminescence spectra are also provided.