Structural Diversity of Bipyridinium-Based Uranyl Coordination Polymers: Synthesis, Characterization, and Ion-Exchange Application
Structural Diversity of Bipyridinium-Based Uranyl Coordination Polymers: Synthesis, Characterization, and Ion-Exchange Application
复制标题
联吡啶鎓基铀酰配位聚合物的结构多样性：合成、表征和离子交换应用
DOI：
10.1021/acs.inorgchem.9b02106
复制
发表时间：
2019
影响因子：
4.6
通讯作者：
Shi Wei-Qun
中科院分区：
文献类型：
--
作者：
Zeng Li-Wen;Hu Kong-Qiu;Mei Lei;Li Fei-Ze;Huang Zhi-Wei;An Shu-Wen;Chai Zhi-Fang;Shi Wei-Qun
联吡啶基作为具有优良电/光致变色和离子交换性能的官能团，已被广泛应用于功能化金属-有机配位聚合物中，但用于构建锕系配位聚合物的尚属罕见。在这项工作中，我们利用以联吡啶为基础的羧酸，1,1 ' -双（4-羧基苯基）-4,4 ' -联吡啶双（氯）（[H2bcbp]Cl2）作为有机配体与铀酰阳离子进行组装。通过引入不同类型的辅助配体和调整pH，通过水热反应合成了5个新型铀酰配位化合物1-5。[(UO2)2(bcbp)(TP)2]·3H2O(1)从铀酰离子和对苯二甲酸（H2TP）和H2bcbp配体开始，具有由对苯二甲酸酯连接的双核单元组成的波浪状二维（2D）结构，并由较长的H2bcbp配体支撑。[(UO2)2(bcbp)(PA)2]·4H2O(2)具有二聚体铀单元之字形链，[(UO2)2(bcbp)(bpdc)2]·5H2O(3)形成一维带状结构。[(UO2)(bcbp)(OH)(H2O)]·Cl(4)和[(UO2)(bcbp)Cl]·Cl(5)的二维结构相似，都是由双核铀酰单元和bcbp2配体构成的。此外，我们还评估了具有阳离子骨架的化合物4去除过氧化物的性能，我们发现化合物4可以在很宽的pH值范围内有效地去除水溶液中的reo4。本研究扩展了紫素衍生物基铀酰配位聚合物的文库，在一定程度上为功能化配体的锕系配位化学提供了更广泛的见解，并可能促进相关配位聚合物的离子交换应用。
As well-known functional groups with excellent electro/photochromic and ion-exchange properties, bipyridinium motifs have been used in functionalized metal–organic coordination polymers, but they are still rarely applied to construct actinide coordination polymers. In this work, we utilized a bipyridinium-based carboxylic acid, 1,1′-bis(4-carboxyphenyl)-4,4′-bipyridinium bis(chloride) ([H2bcbp]Cl2), as the organic ligand to assemble with uranyl cations. By the introduction of different kinds of auxiliary ligands and adjustment of the pH, five novel uranyl coordination compounds,1–5, have been synthesized through hydrothermal reactions. Starting from uranyl ions and terephthalic acid (H2TP) and H2bcbp ligands, [(UO2)2(bcbp)(TP)2]·3H2O (1) has a wave-shaped two-dimensional (2D) structure consisting of dinuclear units connected by terephthalate linkers and further supported by the longer H2bcbp ligands. [(UO2)2(bcbp)(PA)2]·4H2O (2) has a zigzag chain of dimeric uranium units, and [(UO2)2(bcbp)(bpdc)2]·5H2O (3) forms a one-dimensional ribbonlike structure. The 2D structures of [(UO2)(bcbp)(OH)(H2O)]·Cl (4) and [(UO2)(bcbp)Cl]·Cl (5) are similar, both of which are constructed from dinuclear uranyl units and bcbp2–ligands. Furthermore, the performance for perrhenate removal of compound4with a cationic framework is assessed, and we found that compound4can efficiently remove ReO4–from an aqueous solution in a wide range of pH values. This work extends the library of viologen derivative-based uranyl coordination polymers, provides to some extent broader insights into actinide coordination chemistry of functionalized ligands, and may facilitate the ion-exchange applications of related coordination polymers.