College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering , Nanjing Tech University , Nanjing 210009 , P. R. China.
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry , Nanjing University , Nanjing 210093 , P. R. China.
Inorg Chem. 2019 Feb 18;58(4):2463-2470. doi: 10.1021/acs.inorgchem.8b03021. Epub 2019 Feb 4.
The unpredictability of the polyoxometalate (POM) coordination model and the diversity of organic ligands provide more possibilities for the exploration and fabrication of various novel POM-based materials. In this work, a series of POM-based lanthanide (Ln)-Schiff base nanoclusters, [Ln(HO)(DAPSC)][Ln(HO)(DAPSC)][(SiWO)]·15HO (Ln = Sm, 1; Eu, 2; Tb, 3), have been successfully isolated by the reaction of classical Keggin POMs, a Ln ion, and a Schiff-base ligand [2,6-diacetylpyridine bis(semicarbazone), abbreviated as DAPSC]. Both the hindrance effect of the organic ligand and charge balance endow the cluster with fascinating structural features of discrete and linear arrangement. The title compounds with dimensions of ca. 4 × 1 × 1 nm are first trimeric polyoxometalate-based nanosized compounds, constructed by saturated POM anions (SiWO, denoted as SiW). Moreover, the properties (stability, electrochemistry, third-order nonlinear optics, and magnetism) of the compounds have also been studied.
多金属氧酸盐（POM）配位模型的不可预测性和有机配体的多样性为探索和制备各种新型 POM 基材料提供了更多的可能性。在这项工作中，通过经典 Keggin POMs、Ln 离子和希夫碱配体[2,6-二乙酰基吡啶双（缩氨基脲），缩写为 DAPSC]的反应，成功地分离出了一系列基于 POM 的镧系（Ln）-Schiff 基纳米团簇[Ln(HO)(DAPSC)][Ln(HO)(DAPSC)][(SiWO)]·15H2O（Ln = Sm，1；Eu，2；Tb，3）。有机配体的阻碍效应和电荷平衡赋予了配合物离散和线性排列的迷人结构特征。这些尺寸约为 4×1×1nm 的标题化合物是首次由饱和 POM 阴离子（SiWO，表示为 SiW）构建的基于三聚多金属氧酸盐的纳米级化合物。此外，还研究了化合物的性质（稳定性、电化学、三阶非线性光学和磁性）。
