Auxiliary Ligand-Dependent Adaptive Regulation of Uranyl Coordination in Mixed-Ligand Uranyl Compounds of Flexible Biphenyltetracarboxylic Acid
Auxiliary Ligand-Dependent Adaptive Regulation of Uranyl Coordination in Mixed-Ligand Uranyl Compounds of Flexible Biphenyltetracarboxylic Acid
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柔性联苯四甲酸混合配体铀酰化合物中铀酰配位的辅助配体依赖性自适应调节
DOI：
10.1021/acs.inorgchem.0c02904
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发表时间：
2020
影响因子：
4.6
通讯作者：
Mei Lei
中科院分区：
文献类型：
--
作者：
Qian Jun-Feng;Tian Wen-Jiang;Yang Song;Sun Zhong-Hua;Chen Le;Wei Mei-Jun;Wu Zhong;He Ming-Yang;Zhang Zhi-Hui;Mei Lei
混合配体策略是制备新材料和调控材料性能的重要方法之一。本工作通过引入不同的辅助配体（AL），以具有可调正交构象的柔性联苯四甲酸（H4 bptc）为原料，合成了一系列混合配体铀酰配合物（1-6），并研究了不同有机碱分子对H4 bptc与铀酰阳离子配位组装的影响。结果表明，配位的AL（4，4 ′-联吡啶-1，1 ′-二氧化物和1，10-邻菲咯啉）部分占据了铀酰中心的配位位置，直接影响了柔性bptc接头的分子构象和铀酰配位.另一方面，非配位的AL如质子化的4，4 ′-联吡啶（[H2（4，4 ′-bpy）]2+）或二甲基铵以包封的客体或氢键模板的形式作为抗衡离子，也对bptc连接体的构象和配位具有不可忽视的影响。最有趣的是，通过bptc连接体和铀酰中心的配位几何结构，清楚地观察到AL介导的铀酰配位的演变，这表明柔性bptc连接体具有适应性，以采取合适的分子构型和铀酰配位模式，从而适应外部调节剂和变化的环境。讨论了这些铀酰化合物的物理化学特性，特别是光致发光特性，结果表明化合物5具有作为紫外光和X射线辐射的多功能辐射探测材料的潜力。
The mixed-ligand strategy is one of the important methods for preparing new materials and regulating the properties of materials. In this work, by introducing different auxiliary ligands (ALs), we have obtained a series of mixed-ligand uranyl complexes (1–6) from a flexible biphenyltetracarboxylic acid (H4bptc) with an adjustable orthogonal conformation and studied the influence of different organic base molecules on the coordination and assembly of H4bptc with a uranyl cation. It is found that the coordinated ALs, including 4,4′-bipyridine-1,1′-dioxide and 1,10-phenanthroline, partially occupy the coordination sites of the uranyl center and directly affect the molecular conformations and uranyl coordination of flexible bptc linkers. On the other hand, noncoordinated ALs such as protonated 4,4′-bipyridine ([H2(4,4′-bpy)]2+) or dimethylammonium, which work as counterions in the form of encapsulated guests or hydrogen-bonded templates, also have a nonnegligible impact on the conformation and coordination of bptc linkers. Most interestingly, the AL-mediated evolution of uranyl coordination by the bptc linker and coordination geometry of the uranyl center is clearly observed, which suggests the adaptability of flexible bptc linkers to take suitable molecular configurations and uranyl coordination modes so as to adapt to the external regulator agents and varying environment. The physicochemical characterization of these uranyl compounds, especially photoluminescence, is addressed and discussed, and the results reveal that compound5has the potential to serve as a multifunctional radiation detection material for UV light and X-ray radiation.