Copper/Zinc-Directed Heterometallic Uranyl-Organic Polycatenating Frameworks: Synthesis, Characterization, and Anion-Dependent Structural Regulation
Copper/Zinc-Directed Heterometallic Uranyl-Organic Polycatenating Frameworks: Synthesis, Characterization, and Anion-Dependent Structural Regulation
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铜/锌定向异金属铀酰有机多链框架：合成、表征和阴离子依赖性结构调控
DOI：
10.1021/acs.inorgchem.6b00786
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发表时间：
2016
影响因子：
4.6
通讯作者：
Shi Wei-qun
中科院分区：
文献类型：
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作者：
Zhao Ran;Mei Lei;Wang Lin;Chai Zhi-fang;Shi Wei-qun
以2，2 ′-联吡啶-5，5 ′-二甲酸（H2 bpdc）为配体，同时配位O和N，合成了五种铀酰-Cu（II）/Zn（II）配位聚合物：（UO 2）Cu（μ4-bpdc）（μ3-bpdc）（1-Cu），（UO 2）Zn（μ4-bpdc）（μ3-bpdc）（1′-Zn），（UO 2）CuCl（μ3-bpdc）在水热条件下合成了（μ2-Hbpdc）（H2O）（2-Cu）、（UO 2）2Cu 2Cl 2（μ3-bpdc）2（μ2-Hbpdc）2（H2O）3·2 H2O（2-Cu′）和（UO 2）2 Zn（μ3-SO 4）（μ4-bpdc）（μ3-bpdc）（H2O）3（3-Zn）三种配合物。研究了1-Cu、1′-Zn、2-Cu和3-Zn的热稳定性和发光性能。同构化合物1-Cu和1 ′-Zn均具有三维（3D）骨架，该骨架由两组平行的二维（2D）网格以八面体过渡金属阳离子（Cu或Zn）作为交联节点多链连接而成。据我们所知，1-Cu和1 ′-Zn是杂金属铀酰有机配位聚合物中最先出现的两种具有多链网络结构的化合物。化合物2-Cu含有3重互穿的二维网络，这些网络是由[（UO 2）2（bpdc）2（Hbpdc）2]2-二级结构单元和Cu（II）连接而成的。2-Cu′中Cu（II）和Hbpdc-连接的铀酰-bpdc链构成一维倾斜梯形结构。化合物3-Zn呈层状结构，含有一个特殊的[（UO 2）2 Zn（μ3-SO 4）]单元。有趣的是，不同的阴离子可以导致过渡金属阳离子的配位位置的变化，导致杂金属铀酰有机框架的结构多样性。
By employing a multidentate ligand, 2,2′-bipyridine-5,5′-dicarboxylic acid (H2bpdc), with both O-donors and N-donors, five uranyl-Cu(II)/Zn(II) heterometallic coordination polymers, (UO2)Cu(μ4-bpdc)(μ3-bpdc) (1-Cu), (UO2)Zn(μ4-bpdc)(μ3-bpdc) (1′-Zn), (UO2)CuCl(μ3-bpdc)(μ2-Hbpdc)(H2O) (2-Cu), (UO2)2Cu2Cl2(μ3-bpdc)2(μ2-Hbpdc)2(H2O)3·2H2O (2-Cu′), and (UO2)2Zn(μ3-SO4)(μ4-bpdc)(μ3-bpdc)(H2O)3(3-Zn), were prepared under hydrothermal conditions. Thermal stability and luminescent properties of1-Cu,1′-Zn,2-Cu, and3-Znwere also investigated. Isostructural compounds1-Cuand1′-Znboth 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, compounds1-Cuand1′-Znare the first two cases that possess polycatenated networks in heterometallic uranyl-organic coordination polymers. Compound2-Cucontains 3-fold interpenetrated 2D networks which are built by the connection of [(UO2)2(bpdc)2(Hbpdc)2]2–secondary building units and Cu(II). A one-dimensional tilted ladder-like structure in2-Cu′is constructed by uranyl-bpdc chains connected by Cu(II) and Hbpdc–. Compound3-Zndisplays a layered-like 2D network contain an unusual [(UO2)2Zn(μ3-SO4)] 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.