New Perspectives for Old Clusters: Anderson-Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3d-4f Species

作者：Artetxe Benat; Reinoso Santiago; San Felices Leire; Lezama Luis; Gutierez Zorrilla Juan M; Vicent Cristian; Haso Fadi; Liu Tianbo

来源：Chemistry - A European Journal, 2016, 22(13): 4616-4625.

DOI：10.1002/chem.201504768

• cluster compounds
• polyoxometalates
• self-assembly
• supramolecular chemistry
• X-ray diffraction

A series of nine [Sb(7)W(36)O(133)Ln(3)M(2)(OAc)(H2O)(8)](17-) heterometallic anions (Ln(3)M(2); Ln=La-Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3d metal disubstituted Krebs-type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the -Keggin cluster. It is shown, for the first time, that classical Anderson-Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk-shaped species is also revealed. The Ln(3)M(2) anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left- or right-handed orientations. Their ability to self-associate in blackberry-type vesicles in solution has been assessed for the Ce3Co2 derivative.

• 出版日期2016-3-18