Polyoxometalate- supported Y- and YbIII-hydroxo/oxo clusters from carbonate-assisted hydrolysis

被引：112

作者：

Fang, XK

Anderson, TM

Benelli, C

Hill, CL

机构：

[1] Emory Univ, Dept Chem, Atlanta, GA 30322 USA

[2] Univ Florence, Dept Chem, I-50019 Florence, Italy

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2005年 / 11卷 / 02期

关键词：

carbonate; cluster compounds; lanthanides; polyoxometalates; self-assembly;

D O I：

10.1002/chem.200400774

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Carbonate-assisted hydrolysis of Y or Yb-III ions in the presence of the trivacant Wells-Dawson polyoxo-anion, alpha-[P2W15O56](12-), produced two polyoxometalate-supported Y- or Yb-III-hydroxo/oxo clusters, which have been characterized by single-crystal Xray structure determination. The structure of the Y complex consists of a distorted Y-4(OH)(4) cubane cluster encapsulated by two lacunary alpha-[P2W15O56](12-) units, while the Yb cluster features a hexametallic core centered around a mu(6)-oxo atom with each Yb-3(III) triangular face capped by an oxo or a hydroxo group. Magnetization measurements of the ytterbium(III) derivative suggested that intermolecular dipolar exchange is present at low temperatures (below 15 K). Despite its absence in the structures themselves, control experiments show that carbonate not only functions in the hydrolysis, it also influences the structure of the complexes by complexation to yttrium and the f-block elements.

引用

页码：712 / 718

页数：7

共 59 条

[41] Synthesis and characterization of the tetrameric, tri-titanium(IV)-substituted Wells-Dawson-substructure polyoxotungstate, [(P2W15Ti3O60.5)4]36- :: the significance of ultracentrifugation molecular weight measurements in detecting aggregated, anhydride forms of polyoxoanions [J].