Heterometallic Alkaline Earth–Lanthanide BaII–LaIII Microporous Metal–Organic Framework as Bifunctional Luminescent Probes of Al3+ and MnO4–

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• 作者：Bin Ding ; Shi Xin Liu ; Yue Cheng ; Chao Guo ; Xiang Xia Wu ; Jian Hua Guo ; Yuan Yuan Liu ; Yan Li
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4391-4402
• 全文大小：892K
• 年卷期：0
• ISSN：1520-510X

文摘

In this work a rigid asymmetrical tricarboxylate ligand p-terphenyl-3,4″,5-tricarboxylic acid (H₃L) has been employed, and a unique heterometallic alkaline earth–lanthanide microporous luminescent metal–organic framework (MOF) {[Ba₃La_0.5(μ₃-L)_2.5(H₂O)₃(DMF)]·(3DMF)}_n (1·3DMF) (DMF = dimethylformamide) has been isolated under solvothermal conditions. Single-crystal X-ray structural analysis demonstrates that 2D inorganic Ba–O–La connectivity can be observed in 1, which are further bridged via rigid terphenyl backbones of L^3–, forming a unique I²O¹-type microporous luminescent framework. A 1D microporous channel with dimensionality of 9.151(3) Å × 10.098(1) Å can be observed along the crystallographic a axis. PXRD patterns have been investigated indicating pure phases of 1. The luminescence explorations demonstrated that 1 exhibits highly selective and sensitive sensing for Al³⁺ over other cations with high quenching efficiency K_sv value of 1.445 × 10⁴ L·mol^–1 and low detection limit (1.11 μM (S/N = 3)). Meanwhile 1 also exhibits highly selective and sensitive sensing for MnO₄^– over other anions with quenching efficiency K_sv = 7.73 × 10³ L·mol^–1 and low detection limit (0.28 μM (S/N = 3)). It is noted that, when different concentrations of MnO₄^– solutions (0.5 to 100 μM) were dropped into the suspension of 1, the bright blue luminescence of the suspension observed under UV light can gradually change into pink color, indicating visually luminescent sensing, which makes the detection process of MnO₄^– more convenient in practical. The result also reveals that 1 represents the first example of bifunctional heterometallic alkaline earth-lanthanide MOF-based luminescent probes for selectively detecting Al³⁺ and MnO₄^– in the water solutions.