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Published on: June 23, 2023
Copper/Zinc-Directed Heterometallic Uranyl-Organic Polycatenating Frameworks: Synthesis, Characterization, and
Ran Zhao1, Lei Mei1, Lin Wang1
1Laboratory 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.
Abstract:
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 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 [(UO2)2(bpdc)2(Hbpdc)2]2- 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 [(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.
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