title: Ionothermal synthesis of tetranuclear borate clusters containing f- and p-block metals.
abstract: 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 Gd(3+), 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 Pu(3+) and Bi(3+). In addition to detailed structural information, UV/vis-NIR absorption and photoluminescence spectra are also provided.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32306, United States.
authors.forename: T Gannon
authors.initials: TG
authors.lastname: Parker
authors.forename: Amanda L
authors.initials: AL
authors.lastname: Chown
authors.forename: Austin
authors.initials: A
authors.lastname: Beehler
authors.forename: Divya
authors.initials: D
authors.lastname: Pubbi
authors.forename: Justin N
authors.initials: JN
authors.lastname: Cross
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Albrecht-Schmitt