Weng Zhewei, Ren Yuanhang, Gu Min, Yue Bin, He Heyong
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai 200433, P. R. China.
Dalton Trans. 2017 Dec 19;47(1):233-239. doi: 10.1039/c7dt03968a.
Two mixed-addenda Nb/W polyoxometalate (POM)-based hybrid compounds, CuCu(μ-OH)(HO)(trz)·13HO (1) and CuCu(μ-OH)(HO)(Htrz)(trz)·13HO (2), were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction revealed that compound 1 contains planar triangular tricopper {Cu(μ-OH)(trz)} units, and these tricopper units link to each other to form a 1D anti-parallel chain. Cu ions connect the 1D chains by the coordination of trz ligands to form 2D layers in the ab plane. Compound 2 contains the same tricopper {Cu(μ-OH)(trz)} units as well as bicopper {Cu(Htrz)} units. The tricopper units also form 1D chains and the bicopper units connect the 1D chains to form similar 2D layers and finally construct the 3D framework. In both compounds, each Nb/W mixed-addenda Keggin {PWNbO} unit links eight tricopper units to generate the final 3D structure. Magnetism studies indicate anti-ferromagnetic exchange interactions among the Cu ions within the tricopper units, with J values of -209.3 and -200.8 cm in 1 and 2, respectively.
在水热条件下合成了两种基于混合添加剂铌/钨多金属氧酸盐（POM）的杂化化合物，[CuCu(μ-OH)(H₂O)(trz)]₂(PW₉Nb₃O₄₀)·13H₂O (1) 和 [CuCu(μ-OH)(H₂O)(Htrz)(trz)]₂(PW₉Nb₃O₄₀)·13H₂O (2)。单晶X射线衍射表明，化合物1包含平面三角形三铜{Cu(μ-OH)(trz)}单元，这些三铜单元相互连接形成一维反平行链。铜离子通过trz配体的配位连接一维链，在ab平面形成二维层。化合物2包含与三铜{Cu(μ-OH)(trz)}单元相同的单元以及双铜{Cu(Htrz)}单元。三铜单元也形成一维链，双铜单元连接一维链形成类似的二维层，最终构建三维框架。在这两种化合物中，每个铌/钨混合添加剂Keggin{PW₉Nb₃O₄₀}单元连接八个三铜单元以生成最终的三维结构。磁性研究表明，三铜单元内铜离子之间存在反铁磁交换相互作用，在1和2中的J值分别为-209.3和-200.8 cm⁻¹。
