Xu Wei, Ren Ya-Nan, Xie Miao, Zhou Lin-Xia, Zheng Yue-Qing
Joint Laboratory for Environmental Test and Photocatalytic Research of Ningbo University-Zhejiang Zhonghao Applied Engineering Technology Institute Co., Ltd, Research Center of Applied Solid State Chemistry, Chemistry Institute for Synthesis and Green Application, Ningbo University, Ningbo, Zhejiang, 315211 P.R. China.
Dalton Trans. 2018 Mar 28;47(12):4236-4250. doi: 10.1039/c7dt04909a. Epub 2018 Feb 27.
A new series of uranium coordination polymers have been hydrothermally synthesized by using 1,4-naphthalene dicarboxylic acid (HNDC), namely, (HO)[(UO)(NDC)]·HO (1), (H-bpp)[(UO)(NDC)]·EtOH·5HO (2), (H-bpe)[(UO)(NDC)]·EtOH (3), (H-bpp)[(UO)(NDC)]·5HO (4), (H-bpp)[(UO)(HNDC)(NDC)]·2HO (5), and (H-bpy)[(UO)(NDC)] (6) [bpp = 1,3-di(4-pyridyl) propane, bpe = 4,4'-vinylenedipyridine, bpy = 4,4'-bipyridine]. Single-crystal X-ray diffraction demonstrates that complex 1 represents the uranyl-organic polycatenated framework derived from a simple two-dimensional honeycomb grid network structure via a HNDC linker. Complexes 2-4 contain the dinuclear motifs of the two UO pentagonal and one UO hexagonal bipyramids which are linked by NDC anions creating a (UO)(NDC) unit, and further extend to a 2D layer through NDC anions. Complex 5 displays a 1D zigzag double chain structure, in which the carboxylate groups of the NDC anions adopt a chelate mode and further extends to a 2D framework via hydrogen bonds. The 1D structure of complex 6 is similar to the zigzag chain of complex 5. In addition, powder X-ray diffraction, elemental analysis, IR, thermal stability and luminescence properties of all complexes have also been investigated in this paper. The photocatalytic properties of the six complexes for the degradation of tetracycline hydrochloride (TC) under UV irradiation have been examined. Moreover, density functional theory (DFT) calculations were carried out to explore the electronic structural and bonding properties of the uranyl complexes 1-6.
通过使用1,4-萘二甲酸（HNDC）水热合成了一系列新的铀配位聚合物，即(HO)[(UO)(NDC)]·HO (1)、(H-bpp)[(UO)(NDC)]·EtOH·5HO (2)、(H-bpe)[(UO)(NDC)]·EtOH (3)、(H-bpp)[(UO)(NDC)]·5HO (4)、(H-bpp)[(UO)(HNDC)(NDC)]·2HO (5) 和 (H-bpy)[(UO)(NDC)] (6) [bpp = 1,3-二(4-吡啶基)丙烷，bpe = 4,4'-亚乙烯基联吡啶，bpy = 4,4'-联吡啶]。单晶X射线衍射表明，配合物1代表通过HNDC连接体从简单的二维蜂窝状网格网络结构衍生而来的铀酰-有机多链框架。配合物2-4包含两个UO五角双锥和一个UO六角双锥的双核基序，它们通过NDC阴离子连接形成一个(UO)(NDC)单元，并通过NDC阴离子进一步扩展为二维层。配合物5呈现一维锯齿形双链结构，其中NDC阴离子的羧酸根基团采用螯合模式，并通过氢键进一步扩展为二维框架。配合物6的一维结构与配合物5的锯齿链相似。此外，本文还研究了所有配合物的粉末X射线衍射、元素分析、红外光谱、热稳定性和发光性质。考察了这六种配合物在紫外光照射下对盐酸四环素（TC）降解的光催化性能。此外，还进行了密度泛函理论（DFT）计算，以探索铀酰配合物1-6的电子结构和键合性质。
