铀酰配位介导咔唑三羧酸超分子组装体的结构演变
Uranyl Coordination Mediates Structure Evolution of Supramolecular Assemblies of Carbazole Tricarboxylic Acid
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摘要: 作为一类典型的金属-有机框架材料（MOFs），基于锕系金属节点的MOFs具有其独特的锕系-配体键合方式。然而，这些配位相互作用如何参与并影响有机配体的晶格组装过程仍有待研究。在本工作中，以咔唑三羧酸有机配体与铀酰离子的配位组装为例，通过控制合成条件详细研究了铀酰配位作用对咔唑三羧酸配体晶格组装过程的调控。单晶结构分析表明，随着铀酰金属节点的引入，咔唑三羧酸超分子组装体实现了从氢键-有机网络结构向金属-有机网络结构的逐级演变。在这一调控过程中，不同咔唑三羧酸间的连接方式由羧基氢键对逐渐被铀酰配位作用取代，二维网络结构也从六重穿插非平面网络转变为平面超分子网络和金属-有机配位网络。相关转变过程主要表现在羧基不断参与铀酰中心的配位作用，这一过程也得到了红外光谱的证实。通过本工作的开展，成功揭示了铀酰-配体配位作用调控无机-有机多孔材料合成的分子机制及相关材料结构演变的详细过程。Abstract: As a class of typical metal-organic framework materials(MOFs), actinide-based MOFs feature their unique actinide-ligand bonds. However, how these coordination interactions participate in and affect the lattice assembly process of organic ligands remains less studied. In this work, the coordination assembly of carbazole tricarboxylic acid organic ligands and uranyl ions was taken as a showcase study, and the regulation of uranyl coordination on the assembly process of carbazole tricarboxylic acid in lattice by controlling the synthesis conditions was studied in detail. Single-crystal analyses show that with the introduction of uranyl metal nodes, the assembly of carbazole tricarboxylic acid has realized a gradual evolution from a hydrogen bond-organic framework structure to a metal-organic network. In this regulation process, the connection of hydrogen bonds between different carbazole tricarboxylic acids is gradually replaced by uranyl coordination. The two-dimensional network structure also changes from sextuple intercatenated non-planar network through planar supramolecular network to final coordination network. The related transformation process is mainly manifested in gradual participation of the carboxyl groups in the coordination of uranyl center, which has also been confirmed by infrared spectroscopy. This work reveals the molecular mechanism of the synthesis of inorganic-organic porous materials through uranyl-ligand coordination and the detailed process of material structure evolution.
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Keywords:
- actinides /
- uranyl /
- metal-organic framework /
- coordination bonds /
- supramolecular assembly /
- structure regulation
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