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Hydrothermal assembly, structures, topologies, luminescence, and magnetism of a novel series of coordination polymers driven by a trifunctional nicotinic acid building block

Abstract

In this work, a trifunctional N,O-building block, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna), that combines three distinct types of functional groups (COOH, N-pyridyl, and O-ether) was used for the hydrothermal assembly of thirteen new coordination compounds: [Co(μ3-Hcpna)2]n (1), [Mn(μ4-cpna)(H2O)]n (2), [Mn(μ4-cpna)(H2O)2]n (3), [Mn(μ-cpna)(2,2′-bipy)(H2O)2]n (4), {[Ni(μ3-cpna)(2,2′-bipy)(H2O)]2·H2O}n (5), {[Cd(μ3-cpna)(2,2′-bipy)]·2H2O}n (6), [Zn2(µ-cpna)2(2,2′-bipy)2] (7), [Cu(μ-cpna)(2,2′-bipy)(H2O)]n (8), {[Mn(µ-cpna)(phen)2]·6H2O}n (9), {[Ni(µ3-cpna)(phen)(H2O)]·H2O}n (10), [Zn2(µ-cpna)2(phen)2] (11), {[Pb(µ3-cpna)(phen)]·H2O}n (12), and [Ni(μ3-cpna)(4,4′-bipy)0.5(H2O)]n (13). These products were synthesized from the corresponding metal(II) chlorides, H2cpna, NaOH, and optional N-donor supporting ligands or templates {bis(4-pyridyl)amine (bpa), 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy), or 1,10-phenanthroline (phen)}. Products 1–13 were characterized in the solid state by standard methods, including elemental and thermogravimetric analysis (TGA), IR spectroscopy, powder (PXRD) and single-crystal X-ray diffraction. The structures of 1–13 feature distinct structural types, namely the 3D metal-organic frameworks (MOFs 1–3), the 2D coordination polymers (5, 6, 10, 12, and 13), the 1D coordination polymers (4, 8, and 9), and the 0D discrete cyclic dimers (7 and 11). Such a wide structural diversity of 1–13 is driven by various factors, including a type of the metal(II) node, a deprotonation degree of H2cpna, and/or a type of supporting ligand or template. Notably, an addition of bpa can tune the structure of MOF 3 by the template effect. Topological classification of underlying metal-organic networks was performed, leading to several distinct topological nets: rtl (in 1), hxg-d-4-C2/m (in 2), sra (in 3), 2C1 (in 4, 8 and 9), fes (in 5, 10, and 12), hcb (in 6), and 3,4L83 (in 13). Magnetic behavior of 1–5, 8–10, and 13 was studied and theoretically modeled, disclosing antiferromagnetic interactions. Luminescence behavior of 6, 7, 11, and 12 was also investigated.

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Publication details

The article was received on 12 May 2017, accepted on 14 Jul 2017 and first published on 14 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT01742A
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Hydrothermal assembly, structures, topologies, luminescence, and magnetism of a novel series of coordination polymers driven by a trifunctional nicotinic acid building block

    J. Gu, X. Liang, Y. Cai, J. Wu, Z. Shi and A. M. Kirillov, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT01742A

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