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Issue 18, 2017
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Introducing 2-(2-carboxyphenoxy)terephthalic acid as a new versatile building block for design of diverse coordination polymers: synthesis, structural features, luminescence sensing, and magnetism

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Abstract

In this work, an ether-bridged aromatic carboxylic acid, 2-(2-carboxyphenoxy)terephthalic acid (H3cpta), was applied as an unexplored building block for the generation of a novel series of coordination compounds, which represent the first examples of structurally characterized products derived from H3cpta, thus opening up its use as a versatile building block in crystal engineering research. The obtained products were formulated as [Cd(μ-Hcpta)(phen)(H2O)]n (1), [Mn(μ-Hcpta)(phen)(H2O)]n (2), {[Cd33-Hcpta)(μ4-cpta)(μ-Cl)(H2O)4]·2H2O}n (3), {[Cd36-cpta)2(py)2]·5H2O}n (4), [Mn35-cpta)2(2,2′-bipy)2]n (5), [Mn34-cpta)2(phen)3(H2O)2]n (6), {[Zn33-cpta)2(phen)3]·3H2O} (7), [Cd24-cpta)(μ-Cl)(phen)2]n (8), [Cd35-cpta)2(phen)2(H2O)2]n (9), [Cd34-cpta)2(phen)3(H2O)2]n (10), [Cd35-cpta)2(H2biim)2]n (11), [Zn26-cpta)(μ-Hbiim)]n (12), and [Ni33-cpta)2(phen)3(py)3(H2O)3]n (13). These compounds were assembled in the presence of an optional N-donor ancillary ligand, which was selected from 1,10-phenanthroline (phen), pyridine (py), 2,2′-bipyridine (2,2′-bipy), or 2,2′-biimidazole (H2biim). The obtained compounds 1–13 were fully characterized, including by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder (PXRD) and single-crystal X-ray diffraction. The structures of 1–13 vary from a discrete 0D dimer (1) to the 1D (2, 3, 7, and 13) and 2D (5, 6, and 8–11) coordination polymers, as well as to the 3D metal–organic frameworks (MOFs 4 and 12). Such a wide structural diversity of 1–13 is guided by the following factors: a type of metal(II) node and counter anion, a deprotonation degree of the principal H3cpta block, and/or a type of an auxiliary ligand. Topological classification of H-bonded (in 1) and metal–organic (in 2–13) underlying networks was performed, disclosing the following topological types: sql (in 1), 2C1 (in 2 and 7), 3,4,5L45 (in 5, 9, and 11), 3,4L128 (in 6 and 10), 3,3,4L29 (in 8), and SP 1-periodic net (in 13), as well as some topologically unique nets (in 3, 4, and 12). Besides, magnetic properties of 2, 5, 6, and 13 were studied and modeled, revealing antiferromagnetic interactions between adjacent metal(II) centers. In addition, luminescence properties were investigated for 1, 3, 4, and 7–12; MOF 4 can be used as a sensitive material for the detection of Fe3+ ions in aqueous solution through the luminescence quenching effect.

Graphical abstract: Introducing 2-(2-carboxyphenoxy)terephthalic acid as a new versatile building block for design of diverse coordination polymers: synthesis, structural features, luminescence sensing, and magnetism

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Publication details

The article was received on 30 Jan 2017, accepted on 08 Apr 2017 and first published on 10 Apr 2017


Article type: Paper
DOI: 10.1039/C7CE00219J
Citation: CrystEngComm, 2017,19, 2570-2588
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    Introducing 2-(2-carboxyphenoxy)terephthalic acid as a new versatile building block for design of diverse coordination polymers: synthesis, structural features, luminescence sensing, and magnetism

    J. Gu, X. Liang, Y. Cui, J. Wu, Z. Shi and A. M. Kirillov, CrystEngComm, 2017, 19, 2570
    DOI: 10.1039/C7CE00219J

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