posted on 2022-11-02, 21:29authored byYu-Feng Liu, Ke Li, Hui-Yong Lian, Xue-Jiao Chen, Xing-Lei Zhang, Guo-Ping Yang
A novel U(VI)-containing polytungstate (U-POW) tetramer,
{K1.37Na26.63[K2(UO2)4Cl0.5(OH)5.5(γ-SiW10O36)4]}·ca66H2O (U4), was synthesized using the Keggin-type
precursor
[γ-SiW10O36]8– and UO2(NO3)2. U4 was further characterized by single-crystal X-ray diffraction,
FT-IR, Raman spectroscopy, solid-state diffuse reflection spectroscopy,
ICP-OES, ESI-MS, TGA, and PXRD. The central {K2(UO2)4Cl0.5(OH)5.5} chromophore
was constructed dexterously from four uranyl, four halves of K ions,
5.5 bridging μ2-OH, and disordered Cl ions, and was
further stabilized by four {γ-SiW10} moieties to
construct the tetramer [K2(UO2)4Cl0.5(OH)5.5(γ-SiW10O36)4]28–. Notably, U4 could work as an effective bifunctional Lewis
acid-base catalyst for the synthesis of pyrazoles via the condensation of hydrazines with 1,3-diketones under mild conditions,
which is attributed to the synergetic effect of the Lewis acidity
of U(VI) and the Lewis basicity of {γ-SiW10}.