Heterometallic Alkaline Earth-Lanthanide Ba(II)-La(III) Microporous Metal-Organic Framework as Bifunctional Luminescent Probes of Al(3+) and MnO4(.)

Bin Ding; Shi Xin Liu; Yue Cheng; Chao Guo; Xiang Xia Wu; Jian Hua Guo; Yuan Yuan Liu; Yan Li

doi:10.1021/acs.inorgchem.6b00111

Heterometallic Alkaline Earth-Lanthanide Ba(II)-La(III) Microporous Metal-Organic Framework as Bifunctional Luminescent Probes of Al(3+) and MnO4(.)

Inorg Chem. 2016 May 2;55(9):4391-402. doi: 10.1021/acs.inorgchem.6b00111. Epub 2016 Apr 18.

Authors

Bin Ding^{1

2

3}, Shi Xin Liu^{1

2

3}, Yue Cheng^{1

2

3}, Chao Guo^{1

2

3}, Xiang Xia Wu^{1

2

3}, Jian Hua Guo^{1

2}, Yuan Yuan Liu^{1

2

3}, Yan Li^{1

2}

Affiliations

¹ Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University , Tianjin 300387, P. R. China.
² Key Laboratory of Inorganic-Organic Hybrid Functional Materials Chemistry, Tianjin Normal University, Ministry of Education , Tianjin 300387, P. R. China.
³ Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University , Tianjin 300071, China.

PMID: 27088966
DOI: 10.1021/acs.inorgchem.6b00111

Abstract

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) {[Ba3La0.5(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 I(2)O(1)-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 Al(3+) over other cations with high quenching efficiency Ksv value of 1.445 × 10(4) 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 Ksv = 7.73 × 10(3) 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 Al(3+) and MnO4(-) in the water solutions.