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Issue 36, 2018
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Exploring the syntheses, structures, topologies, luminescence sensing and magnetism of Zn(II) and Mn(II) coordination polymers based on a semirigid tricarboxylate ligand

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Abstract

Solvothermal reactions of Zn(II) or Mn(II) salts and 2-(4-carboxyphenoxy)terephthalic acid (H3cpota) in the presence of N-heterocyclic group ligands (1,10-phenanthroline (phen) or 1,4-di(1H-imidazol-1-yl)benzene (bib) or 4,4′-bipyridine (4,4′-bpy)) produced four multi-dimensional coordination polymers, namely, [Mn(μ3-Hcpota)(phen)]n·nH2O 1 (1D), [Mn24-Hcpota)(μ3-Hcpota)(μ2-bib)2(H2O)]n2 (3D), [Zn(μ3-Hcpota)(phen)]n·nH2O 3 (2D), and [Zn24-cpota)(μ2-4,4′-bpy)(μ3-OH)]n·nH2O 4 (3D). Complex 1 features a one-dimensional double ladder formed by synanti carboxylate-bridged dimeric Mn(II) units with 8- and 26-membered rings in an alternating pattern sharing three atoms and gives a (42·6) topology. Complex 2 is formed by linear inorganic chains sharing Mn(II) 8-membered rings in double synsyn carboxylate bridges and H-bond R11(8) alternate modes, which are further connected to each other by two symmetry independent Hcpota2− ligands as well as coordinated bib bridges giving rise to a three-dimensional net with a novel (4·62)(4·68·8)(43·611·8)(43·63) topology. Complex 3 exhibits a two-dimensional layered structure containing 36-membered rings based on 8-membered dinuclear Zn(II) units with (32·44)(34·46·64·7) fes-net topology. The phen and benzoic acid groups are like two kinds of blades in the two sides of the two-dimensional structure of 3. Complex 4 is an interesting three-dimensional (3,8)-connected network including tetranuclear tricyclic [Zn4(OH)2(COO)6] clusters with a new (4·5·6)2(42·56·616·72·82) topology. The semirigid tricarboxylate ligand (H3cpota) shows three geometric modes in the self-assembly of four coordination polymers: a) ‘L’ shape in 1, b) ‘I’ shape in 2 and 3, and c) ‘T’ shape in 4. Magnetization analyses disclose the antiferromagnetic behaviors of 1 and 2. Complexes 3 and 4 feature good solvent stability and can withstand ten common solvents. Luminescence investigations reveal that complex 3 has a highly sensitive, selective, low detection limit and well-recyclable properties in the detection of hexavalent chromium anions in aqueous solution. Quenching mechanisms are also studied in detail.

Graphical abstract: Exploring the syntheses, structures, topologies, luminescence sensing and magnetism of Zn(ii) and Mn(ii) coordination polymers based on a semirigid tricarboxylate ligand

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Publication details

The article was received on 08 Jun 2018, accepted on 02 Aug 2018 and first published on 03 Aug 2018


Article type: Paper
DOI: 10.1039/C8CE00947C
Citation: CrystEngComm, 2018,20, 5442-5456
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    Exploring the syntheses, structures, topologies, luminescence sensing and magnetism of Zn(II) and Mn(II) coordination polymers based on a semirigid tricarboxylate ligand

    S. Li, L. Lu, M. Zhu, S. Feng, F. Su and X. Zhao, CrystEngComm, 2018, 20, 5442
    DOI: 10.1039/C8CE00947C

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