Zhao Ran, Mei Lei, Wang Lin, Chai Zhi-Fang, Shi Wei-Qun
Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
School of Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University , Suzhou 215123, China.
Inorg Chem. 2016 Oct 17;55(20):10125-10134. doi: 10.1021/acs.inorgchem.6b00786. Epub 2016 Sep 28.
By employing a multidentate ligand, 2,2'-bipyridine-5,5'-dicarboxylic acid (Hbpdc), with both O-donors and N-donors, five uranyl-Cu(II)/Zn(II) heterometallic coordination polymers, (UO)Cu(μ-bpdc)(μ-bpdc) (1-Cu), (UO)Zn(μ-bpdc)(μ-bpdc) (1'-Zn), (UO)CuCl(μ-bpdc)(μ-Hbpdc)(HO) (2-Cu), (UO)CuCl(μ-bpdc)(μ-Hbpdc)(HO)·2HO (2-Cu'), and (UO)Zn(μ-SO)(μ-bpdc)(μ-bpdc)(HO) (3-Zn), were prepared under hydrothermal conditions. Thermal stability and luminescent properties of 1-Cu, 1'-Zn, 2-Cu, and 3-Zn were also investigated. Isostructural compounds 1-Cu and 1'-Zn both have a three-dimensional (3D) framework built by polycatenating of two sets of paralleling two-dimensional (2D) grids with octahedral transition metal cations (Cu or Zn) as the cross-linking nodes. As far as we know, compounds 1-Cu and 1'-Zn are the first two cases that possess polycatenated networks in heterometallic uranyl-organic coordination polymers. Compound 2-Cu contains 3-fold interpenetrated 2D networks which are built by the connection of [(UO)(bpdc)(Hbpdc)] secondary building units and Cu(II). A one-dimensional tilted ladder-like structure in 2-Cu' is constructed by uranyl-bpdc chains connected by Cu(II) and Hbpdc. Compound 3-Zn displays a layered-like 2D network contain an unusual [(UO)Zn(μ-SO)] unit. Interestingly, different anions could lead to the change of coordination sites of transition metal cations, resulting in structural diversity of heterometallic uranyl-organic frameworks.
通过使用一种同时含有氧供体和氮供体的多齿配体2,2'-联吡啶-5,5'-二羧酸（Hbpdc），在水热条件下制备了五种铀酰-Cu(II)/Zn(II)异金属配位聚合物，即(UO)Cu(μ-bpdc)(μ-bpdc)（1-Cu）、(UO)Zn(μ-bpdc)(μ-bpdc)（1'-Zn）、(UO)CuCl(μ-bpdc)(μ-Hbpdc)(H₂O)（2-Cu）、(UO)CuCl(μ-bpdc)(μ-Hbpdc)(H₂O)·2H₂O（2-Cu'）和(UO)Zn(μ-SO₄)(μ-bpdc)(μ-bpdc)(H₂O)（3-Zn）。还研究了1-Cu、1'-Zn、2-Cu和3-Zn的热稳定性和发光性质。同构化合物1-Cu和1'-Zn都具有三维（3D）框架结构，该结构由两组平行的二维（2D）网格通过八面体过渡金属阳离子（Cu或Zn）作为交联节点进行多链连接构建而成。据我们所知，化合物1-Cu和1'-Zn是异金属铀酰-有机配位聚合物中首批具有多链连接网络的两个例子。化合物2-Cu包含由[(UO₂)(bpdc)(Hbpdc)]二级结构单元与Cu(II)连接构建而成的3重互穿二维网络。2-Cu'中的一维倾斜梯状结构由通过Cu(II)和Hbpdc连接的铀酰-bpdc链构成。化合物3-Zn呈现出一种层状二维网络，其中包含一个不寻常的[(UO₂)Zn(μ-SO₄)]单元。有趣的是，不同的阴离子会导致过渡金属阳离子配位位点的变化，从而导致异金属铀酰-有机框架结构的多样性。
