Wang Shu-Ju, Li Qian, Xiu Guan-Lin, You Li-Xin, Ding Fu, Van Deun Rik, Dragutan Ileana, Dragutan Valerian, Sun Ya-Guang
Key Laboratory of Inorganic Molecule-Based Chemistry of Liaoning Province, Shenyang University of Chemical Technology, Shenyang 110142, China.
Key Laboratory on Resources Chemicals and Material of Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, China.
Dalton Trans. 2021 Nov 9;50(43):15612-15619. doi: 10.1039/d1dt02687a.
In view of Hg ion sensing by luminescence, a series of new, phenanthroline-decorated 3D lanthanide metal organic frameworks (Ln-MOFs) valorising an original combination of four different lanthanides and two organic ligands, thiobis(4-methylene-benzoic acid) (Htmba) and 1,10-phenanthroline (phen), have been successfully synthesized, namely {[Ln(tmba)(phen)]·(HO)(phen)} [Ln = Ce, = 3 (1); Pr, = 1 (2); Eu, = 3 (3); and Tb, = 3 (4)]. Compounds 1-4 were characterised by single-crystal X-ray diffraction, elemental and thermogravimetric analyses, and powder X-ray diffraction. The luminescence properties of complexes 3 and 4 were thoroughly investigated. It is herein proved that compound 3 sensitively and selectively acts as an excellent luminescent probe for the detection of Hg ions in waters, with a detection limit of 1.00 μM. As additional assets, 3 displays superb stability over a wide pH range (3-12) of the aqueous media, as well as convenient recycling after completion of the detection experiments. The rationale for the observed luminescence quenching effect of mercury might be a strong interaction arising between Hg ions and the carboxylate oxygen atoms of the tmba ligand. The results open new perspectives for applications in environmental remediation.
鉴于通过发光进行汞离子传感，一系列新型的、用菲咯啉修饰的三维镧系金属有机框架（Ln-MOFs）已成功合成，这些框架采用了四种不同镧系元素与两种有机配体（硫代双（4-亚甲基苯甲酸）（Htmba）和1,10-菲咯啉（phen））的原始组合，即{[Ln(tmba)(phen)]·(H₂O)(phen)} [Ln = Ce，ν = 3 (1)；Pr，ν = 1 (2)；Eu，ν = 3 (3)；Tb，ν = 3 (4)]。化合物1 - 4通过单晶X射线衍射、元素分析和热重分析以及粉末X射线衍射进行了表征。对配合物3和4的发光性质进行了深入研究。本文证明化合物3作为一种灵敏且选择性的优秀发光探针，可用于检测水中的汞离子，检测限为1.00 μM。此外，3在水介质的宽pH范围（3 - 12）内显示出极好的稳定性，并且在检测实验完成后便于回收利用。观察到的汞发光猝灭效应的原理可能是Hg离子与tmba配体的羧酸根氧原子之间产生的强相互作用。这些结果为环境修复应用开辟了新的前景。
