Modular Assembly of Isostructural Mixed-Ligand Uranyl Coordination Polymers Based on a Patterning Strategy
Modular Assembly of Isostructural Mixed-Ligand Uranyl Coordination Polymers Based on a Patterning Strategy
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基于图案化策略的同结构混合配体铀酰配位聚合物的模块化组装
DOI：
10.1021/acs.inorgchem.2c00853
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发表时间：
2022
影响因子：
4.6
通讯作者：
Shi Wei-Qun
中科院分区：
文献类型：
--
作者：
Geng Jun-Shan;Feng Wen;Li Jie;Tang Xiao-Yi;Meng Liao;Yu Ji-Pan;Hu Kong-Qiu;Yuan Li-Hua;Mei Lei;Shi Wei-Qun
控制分子结构单元的有序组装以形成所需的结构，化学和物理性质的固态材料仍然是一个长期的目标，值得研究。在这项工作中，我们提出了一种模式化的策略，通过组合具有互补的分子几何形状和良好匹配的配位模式的有机配体对的混合配体铀酰配位聚合物（CPs）的模块化组装和结构调控。通过使用5-（对甲苯基二氮烯基）三氮烯二酸配体（H2 ptdi）与不同的刚性线性双羧酸连接体构建了一个明确的梯形结构，得到了五种新型的同构铀酰配位聚合物，[（UO）2（ptdi）（bdc）0.5（dma）（1），[（UO）2（ptdi）（bpdc）0.5（dma）（2），[（UO）2（ptdi）（tpdc）0.5（dma）（3），[（UO）2（ptdi）（ndc）0.5（dma）（4）和[（UO）2（ptdi）（pdc）0.5（dma）（5）{H2 bdc，1，4-二羧基苯; H2 bpdc，4，4 ′-联苯二甲酸; H2 tpdc，三联苯-4，4 ″-二甲酸; H2 ndc，2，6-萘二甲酸; H2 pdc，1，6-芘二甲酸;[dma+，[（CH 3）2 NH 2 +}的合成。结构分析表明，1-5具有相似的梯形单元，但由于连接体的长度和宽度不同，一维纳米通道和层间距的大小不同。由于这些同构阳离子框架的层间距的变化，观察到Eu 3+与[dma+]的离子交换性能的差异。并通过热重分析、红外光谱、荧光光谱、元素分析、PXRD和紫外光谱等手段对具有高相纯度的化合物进行了表征。其中，化合物3具有较强的荧光，可选择性地检测水溶液中的Fe 3+，而不是几种竞争金属阳离子。该工作不仅为有效调控功能配位聚合物的模块化合成提供了一种可行的图案化方法，而且丰富了具有有趣结构和功能的铀酰基配位聚合物库。
Controlling the orderly assembly of molecular building blocks for the formation of the desired architectural, chemical, and physical properties of the resulting solid-state materials remains a long-term goal and deserves to be examined. In this work, we propose a patterning strategy for modular assembly and structural regulation of mixed-ligand uranyl coordination polymers (CPs) through the combination of couples of organic ligands with complementary molecular geometry and well-matched coordination modes. By using a 5-(p-tolyldiazenyl)isophthalic acid ligand (H2ptdi) with different rigid linear bicarboxylic acid linkers to construct a well-defined ladder-like pattern, five novel isostructural uranyl coordination polymers, [(UO)2(ptdi)(bdc)0.5(dma) (1), [(UO)2(ptdi)(bpdc)0.5(dma) (2), [(UO)2(ptdi)(tpdc)0.5(dma) (3), [(UO)2(ptdi)(ndc)0.5(dma) (4), and [(UO)2(ptdi) (pdc)0.5(dma) (5) {H2bdc, 1,4-dicarboxybenzene; H2bpdc, 4,4'-biphenyldicarboxylic acid; H2tpdc, terphenyl-4,4″-dicarboxylic acid; H2ndc, 2,6-naphthalenedicarboxylic acid; H2pdc, 1,6-pyrenedicarboxylic acid; [dma+, [(CH3)2NH2+}, were successfully synthesized. Structural analysis reveals that 1-5 have similar ladder-like units but different sizes of one-dimensional nanochannels and interlayer spacing due to the different lengths and widths of the linkers. Because of the changes in interlayer spacing of these isostructural cationic frameworks, differences in the performance of Eu3+ ion exchange with [dma+ are observed. Moreover, those compounds with high phase purity have been further characterized by thermogravimetric analysis, infrared spectroscopy, and luminescence spectroscopy, element analysis, PXRD and UV spectroscopy. Among them, compound 3 with strong fluorescence can selectively detect Fe3+ over several competing metal cations in aqueous solution. This work not only provides a feasible patterning method for effectively regulating the modular synthesis of functional coordination polymers but also enriches the library of uranyl-based coordination polymers with intriguing structures and functionality.