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Efficient luminescence sensing in two lanthanide metal–organic frameworks with rich uncoordinated Lewis basic sites
CrystEngComm ( IF 2.6 ) Pub Date : 2021-08-12 , DOI: 10.1039/d1ce00923k
Liming Deng 1, 2 , Huihui Zhao 1 , Kang Liu 1 , Dingxuan Ma 1
Affiliation  

Developing highly sensitive MOF-based probes for environmental contaminant detection is of much importance and challenging. Here, two new three-dimensional lanthanide metal–organic frameworks (Ln-MOFs), {[Eu(DTA)1.5(H2O)]·H2O}n (Eu-DTA) and [Tb(DTA)(C2O4)0.5(H2O)]n (Tb-DTA) (H2DTA = 2,5-di(1H-imidazol-1-yl)terephthalic acid), are successfully synthesized via a hydrothermal reaction. Single-crystal X-ray diffraction analyses demonstrate that the extended π conjugated ligand plays an important role in the coordination mode and topologies. Eu-DTA possesses a 4,6-connected three-dimensional topological structure, while Tb-DTA exhibits a 4,5-connected three-dimensional framework. Interestingly, the rich uncoordinated nitrogen or oxygen atoms in these two structures can be used as Lewis basic sites, showing strong sensitivity to metal ions and solvent molecules. Furthermore, luminescence and sensing studies reveal that Eu-DTA and Tb-DTA can sensitively and simultaneously detect Fe3+ ions and nitrobenzene, which suggests that the two Ln-MOFs are promising bifunctional luminescence sensors. The quenching mechanism for Fe3+ has been discussed in detail.

中文翻译:

具有丰富的不配位路易斯碱性位点的两种镧系金属-有机骨架中的高效发光传感

开发用于环境污染物检测的高灵敏度 MOF 探针非常重要且具有挑战性。在这里,两个新的三维镧系元素金属有机骨架 (Ln-MOFs),{[Eu(DTA) 1.5 (H 2 O)]·H 2 O} n (Eu-DTA) 和 [Tb(DTA)(C 2 O 4 ) 0.5 (H 2 O)] n (Tb-DTA) (H 2 DTA = 2,5-di(1 H -imidazol-1-yl)terephthalic acid),通过水热反应。单晶 X 射线衍射分析表明,扩展的 π 共轭配体在配位模式和拓扑结构中起着重要作用。Eu-DTA 具有 4,6-connected 三维拓扑结构,而 Tb-DTA 具有 4,5-connected 三维结构。有趣的是,这两种结构中丰富的未配位氮或氧原子可以作为路易斯碱位点,对金属离子和溶剂分子表现出很强的敏感性。此外,发光和传感研究表明,Eu-DTA 和 Tb-DTA 可以灵敏地同时检测 Fe 3+离子和硝基苯,这表明这两种 Ln-MOF 是很有前途的双功能发光传感器。Fe 3+的淬火机理 已经详细讨论过了。
更新日期:2021-09-06
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