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Series of Cadmium(II) Coordination Polymers Based on a Versatile Multi-N-Donor Tecton or Mixed Carboxylate Ligands: Synthesis, Structure, and Selectively Sensing Property.

ABSTRACT: Five Cd(II) metal-organic frameworks (MOFs), [Cd(HL)₂] (1), [Cd(HL)₂(H₂O)₂] (2), [Cd₃(HL)₂(obda)₂] (3), [Cd₂(HL)₂(ohmbda)(DMA)(H₂O)] (4), and [Cd₂(HL)(btc)(H₂O)₂]·3H₂O (5), were prepared by reactions of Cd(NO₃)₂·4H₂O with 1-(1H-imidazol-4-yl)-4-(4H-tetrazol-5-yl)benzene (H₂L) or mixed carboxylate ancillary ligands of 1,2-benzenedicarboxylic acid (H₂obda), 5-hydroxy-1,3-benzenedicarboxylic acid (H₂ohmbda), and 1,3,5-benzenetricarboxylic acid (H₃btc), respectively. Their structures have been characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy (IR), thermogravimetric analysis, and powder X-ray diffraction. Compounds 1 and 2 are supramolecular isomeric frameworks without consideration of the solvent molecules. Complex 1 exhibits a binodal (3, 5)-connected two-dimensional (2D) layer structure with the point (Schläfli) symbol of (5²·6)(5⁵·6⁴·7), while complex 2 shows a 2D + 2D ? 3D (three-dimensional) framework. Complex 3 is a (3, 5, 6)-connected tetranodal 3D net with the point (Schläfli) symbol of (4·8²)₂(4⁵·6·8⁴)₂(4⁵·6⁵)₂(4⁸·6⁶·8). Compound 4 is a (3, 3, 8)-connected trinodal 3D net with the point (Schläfli) symbol based on a binuclear [Cd₂N₂O] subunit, while 5 is a 2-nodal (3, 4)-connected 2D V₂O₅-type network based on [Cd₂N₂(COO)₂] SBU. The studies of molecular sensing properties show that the luminescent MOFs can be employed as fluorescent sensors for the detection of Fe³⁺ and nitro compounds. Compound 1 and 3 exhibit quenching responses for Fe³⁺ in dimethylformamide solution with detection limits of 2.3 × 10^-6 and 8.6 × 10^-7 M, respectively. Meanwhile, compound 5 can sense 4-nitrophenol with a detection limit as low as 5.75 × 10^-7 M.

SUBMITTER: Guo XZ

PROVIDER: S-EPMC6682020 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Series of Cadmium(II) Coordination Polymers Based on a Versatile Multi-N-Donor Tecton or Mixed Carboxylate Ligands: Synthesis, Structure, and Selectively Sensing Property.

Guo Xing-Zhe XZ Chen Shui-Sheng SS Li Wei-Dong WD Han Shuai-Shuai SS Deng Feng F Qiao Rui R Zhao Yue Y

ACS omega 20190702 7

Five Cd(II) metal-organic frameworks (MOFs), [Cd(HL)2] (1), [Cd(HL)2(H2O)2] (2), [Cd3(HL)2(obda)2] (3), [Cd2(HL)2(ohmbda)(DMA)(H2O)] (4), and [Cd2(HL)(btc)(H2O)2]·3H2O (5), were prepared by reactions of Cd(NO3)2·4H2O with 1-(1H-imidazol-4-yl)-4-(4H-tetrazol-5-yl)b ...[more]

PMID: 31460260

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Project description:BACKGROUND: Lead is a heavy toxic metal element in biological systems and is one of the major pollutants as a result of its widespread use in industries. In spite of its negative roles the coordination chemistry of Pb(II) complexes is a matter of interest. The N,N'-bidentate aromatic bases such as BPY,4-BPY and PHEN (BPY?=?2,2'bipyridine, 4-BPY?=?4,4'-dimethyl-2,2'-bipyridine, PHEN?=?1,10-Phenanthroline) are widely used to build supramolecular architectures because of their excellent coordinating ability and large conjugated system that can easily form ?-? interactions among their aromatic moieties. A series of novel Pb(II) complexes in concert with 5-CTPC, 5-BTPC (5-CTPC?=?5-chlorothiophen-2-carboxylate, 5-BTPC?=?5-bromothiophen-2-carboxylate) and corresponding bidentate chelating N.N' ligands have been synthesized and characterized. RESULTS: Five new Pb (II) complexes [Pb(BPY)(5-CTPC)2] (1), [Pb(4-BPY)(5-CTPC)2] (2), [Pb2(PHEN)2(5-CTPC)4] (3), [Pb(4-BPY)(5-BTPC)2] (4) and [Pb2(PHEN)2(5-BTPC)2(ACE)2] (5) have been synthesized. Even though in all these complexes the molar ratio of Pb, carboxylate, N,N-chelating ligand are the same (1:2:1), there is a significant structural diversity. These complexes have been characterised and investigated by elemental analysis, IR, 1H-NMR,13C-NMR, TGA, and photoluminescence studies. Single crystal X-ray diffraction studies reveal that complexes (1, 2) and (4) are mononuclear while (3 and 5) are dinuclear in nature which may result from the chelating nature of the ligands, various coordination modes of the carboxylates, and the coordination geometry of the Pb(II) ions. CONCLUSIONS: The observation of structures 2,4 and 3,5 show the structural changes made just chloro/bromo substituent of the thiophene ring. A detailed packing analysis has been undertaken to delineate the role of valuable non covalent interactions like X…?, H…X, (X?=?Cl/Br). A quadruple hydrogen bond linking the monomeric units and generating a supramolecular architecture is observed in (1). The metal bite unit comprised of PbN2C2 (i.e. Pb-N-C-C-N-Pb) is the repeating unit in all the five complexes and they have almost same geometrical parameters. This metal bite has been identified as the self assembly unit in complexes.

Dataset Information

Series of Cadmium(II) Coordination Polymers Based on a Versatile Multi-N-Donor Tecton or Mixed Carboxylate Ligands: Synthesis, Structure, and Selectively Sensing Property.

Publications

Series of Cadmium(II) Coordination Polymers Based on a Versatile Multi-N-Donor Tecton or Mixed Carboxylate Ligands: Synthesis, Structure, and Selectively Sensing Property.

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