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Bringing 5-(3,4-dicarboxylphenyl)picolinic acid to crystal engineering research: Hydrothermal assembly, structural features, and photocatalytic activity of Mn, Ni, Cu, and Zn coordination polymers

Abstract

5-(3,4-Dicarboxylphenyl)picolinic acid (H3dppa) was applied as a novel tricarboxylic acid spacer with phthalate and picolinate functionalities for the aqueous-medium assembly of seven new coordination compounds, namely, [Mn2(μ-Hdppa)2(phen)2(H2O)2] (1), {[Mn(μ-Hdppa)(2,2′-H2biim)(H2O)]·H2O}n (2), [Ni(Hdppa)(phen)2]·4H2O (3), {[Ni(μ-Hdppa)(μ-4,4′-bipy)(H2O)]·H2O}n (4), {[Cu3(µ3-dppa)(µ-Hdppa)(phen)4]2[Cu(µ-Hdppa)2]·10H2O}n (5), {[Ni3(μ-dppa)2(µ-1,4-bpb)2(H2O)6]·4H2O}n (6), and {[Zn3(μ4-dppa)2(phen)2(H2O)2]·4H2O}n (7). These products 1–7 represent the first structurally characterized examples of the coordination compounds derived from H3dppa. Compounds 1–7 were assembled in the presence of various N-donor supporting ligands acting as crystallization mediators, which were selected from 1,10-phenanthroline (phen), 2,2′-biimidazole (H2biim), 4,4′-bipyridine (4,4′-bipy), or 1,4-bis(pyrid-4-yl)benzene (1,4-bpb). Full characterization of 1–7 by IR spectroscopy, thermogravimetric (TGA), elemental, and topological analysis, as well as powder (PXRD) and single-crystal X-ray diffraction was performed. The structural types range from the discrete 0D complexes (1 and 3) and the 1D coordination polymers with 2C1 topology (2, 5, and 6) to the 2D metal-organic layers with sql topology (4 and 7). The structural diversity of 1–7 is driven by various factors, including a nature of metal(II) node, a deprotonation degree of H3dppa, or a type of crystallization mediator. Magnetic properties of 1, 2, 4, and 6 were studied and modeled, revealing antiferromagnetic (in 1, 2, and 6) or ferromagnetic (in 4) interactions between adjacent metal(II) centers. Luminescence of 7 was also investigated. Moreover, photocatalytic activity of 1–7 was studied for the degradation of methylene blue as a model dye pollutant, disclosing that the nickel(II) coordination polymer 4 is the most active catalyst. The observed catalytic activity of 1–7 well correlates with their band gap energies determined by the UV-diffuse reflectance method.

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Publication details

The article was received on 20 Nov 2017, accepted on 29 Dec 2017 and first published on 29 Dec 2017


Article type: Paper
DOI: 10.1039/C7CE02009K
Citation: CrystEngComm, 2017, Accepted Manuscript
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    Bringing 5-(3,4-dicarboxylphenyl)picolinic acid to crystal engineering research: Hydrothermal assembly, structural features, and photocatalytic activity of Mn, Ni, Cu, and Zn coordination polymers

    J. Gu, Y. Cai, X. Liang, J. Wu, Z. Shi and A. Kirillov, CrystEngComm, 2017, Accepted Manuscript , DOI: 10.1039/C7CE02009K

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