Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2025 Feb 28;18(5):1089.
doi: 10.3390/ma18051089.

Roles of Water Molecules in the Structures and Magnetic Properties of Coordination Polymers with a Dicarboxylate Ligand

Dehui Zong  1 , En-Qing Gao  1 , Dawei Zhang  1
Affiliations

Roles of Water Molecules in the Structures and Magnetic Properties of Coordination Polymers with a Dicarboxylate Ligand

Dehui Zong et al. Materials (Basel). .

Abstract

Three new coordination polymers, {[M(nbpdc)(DMF)(H2O)2]·H2O}∞ (M = Co and Ni) and [Zn(nbpdc)(DMF)(H2O)]∞, were synthesized from 2-nitrobiphenyl-4,4'-dicarboxylate (nbpdc2-). The isomorphous Co(II) and Ni(II) compounds exhibited a two-dimensional coordination network in which the chains with single-water bridges and the chains with single-nbpdc2- bridges intersected each other by sharing the metal ions. The coordination networks were connected with uncoordinated water molecules through hydrogen bonds. The rarely identified single-water-bridged coordination chain was reinforced by water-based intrachain hydrogen bonds. The single-water bridges mediated modest antiferromagnetic superexchange in both Co(II) and Ni(II) compounds and afforded a spin-canting structure for the Co(II) compound at low temperatures. Water molecules played a distinct structural role in the Zn(II) compound, which was a one-dimensional coordination polymer with single-nbpdc2- bridges. Instead of bridging metal ions, each water molecule was coordinated to one metal ion and hydrogen-bonded to the coordination spheres of other two metal ions, resulting to an infinite ladderlike hydrogen-bonding motif. The ladders interlinked the nbpdc-bridged chains into a three-dimensional supramolecular architecture featuring the 5-conneted {44.64} net.

Keywords: cobalt; coordination polymers; hydrogen bonds; magnetic properties; nickel; spin canting; water bridges.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
PXRD profiles of 1–3 compared with those simulated from the crystal data of 1 and 2.
Figure 2
Figure 2
Crystal structure of 1. (a) A view of the coordination chain formed from Zn(II) and nbpdc2− (ellipsoidal probability: 50%). The hydrogen atoms of nbpdc2− and DMF have been omitted for clarity. (b) The hydrogen-bonded ladderlike motif. (c) A view showing the stacking of the coordination chains through hydrogen bonds. The non-oxygen atoms of DMF and the nitro groups and hydrogen atoms of nbpdc2− have been omitted for clarity. (d) A topologic representation of the 3D structure composed of coordination chains (red) and hydrogen-bonded ladders (blue).
Figure 3
Figure 3
Crystal structure of 2. (a) A view of the coordination modes of Co(II) and nbpdc2− (ellipsoidal probability: 50%). The nitro group disordered over two positions is shown in light color and the hydrogen atoms of nbpdc2− and DMF have been omitted for clarity. (b) A water-bridged chain assisted with hydrogen bonds. (c) A 2D coordination layer. The non-oxygen atoms of DMF and the nitro groups and hydrogen atoms of nbpdc2− have been omitted for clarity. (d) A view of the layer packing showing interlayer hydrogen bonding. The hydrogen atoms of nbpdc2− and DMF have been omitted for clarity.
Figure 4
Figure 4
(a) Temperature dependence of χ and χT of 2 under 1 kOe. The black and red solid lines both represent the best fit to Equation (1) in the text. (b) Isothermal magnetization of 2 at 2 K. (c) FC and ZFC susceptibility of 2 under different field. (d) χ′(T) and χ″(T) plots for 2 at frequencies 10–1000 Hz with Hdc = 0 and Hac = 3.5 Oe.
Figure 5
Figure 5
Temperature dependence of χ and χT for 3 under 1 kOe. Both solid lines represent the best fit to Equation (2) in the text.
See this image and copyright information in PMC

References

    1. Li L., Lin R.-B., Krishna R., Li H., Xiang S., Wu H., Li J., Zhou W., Chen B. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites. Science. 2018;362:443–446. doi: 10.1126/science.aat0586. - DOI - PubMed
    1. Lippi M., Cametti M. Highly dynamic 1D coordination polymers for adsorption and separation applications. Coord. Chem. Rev. 2021;430:213661. doi: 10.1016/j.ccr.2020.213661. - DOI
    1. You L.-X., Ren B.-Y., He Y.-K., Wang S.-J., Sun Y.-G., Dragutan V., Xiong G., Ding F. Structural features of lanthanide coordination polymers with catalytic properties. J. Mol. Struct. 2024;1304:137687. doi: 10.1016/j.molstruc.2024.137687. - DOI
    1. Jiao L., Wang Y., Jiang H.-L., Xu Q. Metal–Organic Frameworks as Platforms for Catalytic Applications. Adv. Mater. 2018;30:1703663. doi: 10.1002/adma.201703663. - DOI - PubMed
    1. Wang H.-N., Meng X., Dong L.-Z., Chen Y., Li S.-L., Lan Y.-Q. Coordination polymer-based conductive materials: Ionic conductivity vs. electronic conductivity. J. Mater. Chem. A. 2019;7:24059–24091. doi: 10.1039/C9TA08253K. - DOI

LinkOut - more resources