Bipyridine-Directed Syntheses of Uranyl Compounds Containing Semirigid Dicarboxylate Linkers: Diversity and Consistency in Uranyl Speciation
Bipyridine-Directed Syntheses of Uranyl Compounds Containing Semirigid Dicarboxylate Linkers: Diversity and Consistency in Uranyl Speciation
复制标题
联吡啶直接合成含有半刚性二羧酸酯连接体的铀酰化合物：铀酰形态的多样性和一致性
DOI：
10.1021/acs.inorgchem.9b00452
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：
An Shu-wen;Mei Lei;Hu Kong-qiu;Li Fei-ze;Xia Chuan-qin;Chai Zhi-fang;Shi Wei-qun
联吡啶类有机碱在合成新型铀酰-有机杂化材料中具有重要的应用价值，但其分子结构与其作为结构导向剂的作用之间的关系，特别是对于半刚性二元羧酸体系的作用，目前尚不清楚。在本文中，我们利用一系列联吡啶配体，1，10-菲咯啉（phen）、2，2 ′-联吡啶（bipyridine）和4，4 ′-二羧基联苯砜（H2 dbsf），研究了联吡啶配体如何引导铀酰有机化合物与半刚性二羧酸连接基的配位组装（2，2 ′-bpy）、5，5 ′-二甲基联吡啶（5，5 ′-dmbpy）、4，4 ′-联吡啶（4，4 ′-bpy）或1，3-二（4-吡啶基）丙烷（bpp）。在水热条件下合成了8种铀酰有机配位聚合物，其中4种为[[UO 2（dbsf）（phen）]（1），[UO 2（dbsf）（phen）]·H2O（1′），[U4 O 10（dbsf）3]2[H2 bpp]2（6），[U4 O 10（dbsf）3]2[H2 bpp]（6′）]，根据联吡啶配体的螯合或模板作用，将其分为两类：1，1 ′，[UO 2（dbsf）]（2，2 ′-bpy）]（2）和[（UO 2）2（dbsf）2（5，5 ′-dmbpy）2]（3）是具有联吡啶配体的弹簧状三股螺旋（phen，2，2 ′-bpy，或5，5 ′-dmbpy）作为螯合配体，而[U_4O_（10）（dbsf）_3][H_2（4，4 ′-bpy）]（4）、[U4 O 10（dbsf）3]2[H（4，4 ′-bpy）]2[Ni（H2O）6]（5）、6和6 ′是以4，4 ′-bpy或bpp为模板配体和电荷平衡剂的四核铀酰介导的双层互穿网络。不同的联吡啶配体参与或不参与铀酰配位不仅促进了不同类型有机碱之间铀酰形态和最终拓扑结构的多样性，而且促进了相同类型联吡啶配体的一致性，从而赋予了在谨慎选择联吡啶配体的帮助下合理设计基于半刚性二羧酸配体的UCP的可能性。
Bipyridine organic bases are beneficial to the synthesis of novel uranyl–organic hybrid materials, but the relationship between their molecular structures and specific roles as structure-directing agents, especially for the semirigid dicarboxylate systems, is still unclear. Here we demonstrate how the bipyridine ligands direct the coordination assembly of uranyl–organic compounds with a semirigid dicarboxylate linker, 4,4′-dicarboxybiphenyl sulfone (H2dbsf), by utilizing a series of bipyridine ligands, 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bpy), 5,5′-dimethylbipyridine (5,5′-dmbpy), 4,4′-bipyridine (4,4′-bpy), or 1,3-di(4-pyridyl)propane (bpp). Under hydrothermal conditions, eight uranyl–organic coordination polymers (UCPs), four of which [[UO2(dbsf)(phen)] (1), [UO2(dbsf)(phen)]·H2O (1′), [U4O10(dbsf)3]2[H2bpp]2(6), and [U4O10(dbsf)3]2[H2bpp] (6′)] were reported previously, were synthesized and divided into two types based on the chelate or template effect of these bipyridine ligands.1,1′, [UO2(dbsf)(2,2′-bpy)] (2), and [(UO2)2(dbsf)2(5,5′-dmbpy)2] (3) are springlike triple helices with bipyridine ligands (phen, 2,2′-bpy, or 5,5′-dmbpy) as chelate ligands, while [U4O10(dbsf)3][H2(4,4′-bpy)] (4), [U4O10(dbsf)3]2[H(4,4′-bpy)]2[Ni(H2O)6] (5),6, and6′are tetranuclear uranyl-mediated 2-fold-interpenetrating networks with 4,4′-bpy or bpp as template ligands and charge-balancing agents. The participation or not in uranyl coordination of different bipyridine ligands promotes not only diversity in uranyl speciation and final topological structures among different classes of organic bases but also consistency for the same types of bipyridine ligands, which thus endows the possibility of the rational design of UCPs based on semirigid dicarboxylate ligands with the aid of cautiously selected bipyridine ligands.