Coordination polymers containing a pyrazole-based ligand and 4,4′-bipyridine as a spacer: enhancing the family of nonzero-dimensional compounds featuring single-ion magnetic behavior

doi:10.1016/j.inoche.2020.108201

Inorganic Chemistry Communications

Volume 121, November 2020, 108201

https://doi.org/10.1016/j.inoche.2020.108201 Get rights and content

Highlights

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Two 1D-coordination polymers containing a pyrazole-based ligand and 4,4′-bipy.
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Predominant ferromagnetic interactions in the copper-based compound.
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ZFS effects are important for magnetic behavior of cobalt(II) polymer.
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CASSCF calculations determined the sign of the axial component of the ZFS.
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Slow relaxation of the magnetization and a single-ion magnet behavior.

Abstract

Two coordination polymers with molecular formula ¹_∞[M(L)₂(4,4′-bipy)(H₂O)₂], where M stands for Co^II (1) or Cu^II, (2), and L = 5-amino-1-phenyl-1H-pyrazole-4-carboxylate ligand were obtained by slow solvent diffusion and characterized by spectroscopic techniques, single crystal and powder X-ray diffraction, magnetic measurements, and DFT calculations. Magnetic studies carried out for complex 1 showed the key role played by the zero-field splitting and the experimental fit parameters were correlated to CASSCF calculations. Moreover, AC magnetic measurements for 1 revealed a field-induced slow relaxation of the magnetization and a single-ion magnet behavior. For the copper-containing polymer, two kinds of magnetic interactions were observed in the magnetic data and confirmed by using broken-symmetry DFT calculations: (i) ferromagnetic interchain coupling mediated by the hydrogen-bonds and (ii) antiferromagnetic intrachain interaction through the 4,4′-bipy ligand.

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Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors acknowledge the financial support from Fundação Carlos Chagas de Amparo à Pesquisa do Estado do Rio de Janeiro - FAPERJ (project numbers E-26/202.720/2018, E-26/211.091/2019 and E-26/010.000978/2019), Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq (project numbers 446186/2014-7 and 423086/2018-9) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES), within the Capes-PrInt program, financial code 001 (project number 88887.

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Cited by (2)

Crystal structures and Hirshfeld surface analysis of 5-amino-1-(4-methoxyphenyl)pyrazole-4-carbox-ylic acid and 5-amino-3-(4-methoxyphenyl)-isoxazole
2022, Acta Crystallographica Section E: Crystallographic Communications
The title compounds, C₁₁H₁₁N₃O₃, (I), and C₁₀H₁₀N₂O₂, (II), are commercially available and were crystallized from ethyl acetate solution. The dihedral angle between the pyrazole and phenyl rings in (I) is 52.34 (7)° and the equivalent angle between the isoxazole and phenyl rings in (II) is 7.30 (13)°. In the crystal of (I), the molecules form carboxylic acid inversion dimers with an R(8) ring motif via pairwise O—H⋯O hydrogen bonds. In the crystal of (II), the molecules are linked via N—H⋯N hydrogen bonds forming chains propagating along [010] with a C(5) motif. A weak N—H⋯π interaction also features in the packing of (II). Hirshfeld surface analysis was used to explore the intermolecular contacts in the crystals of both title compounds: the most important contacts for (I) are H⋯H (41.5%) and O⋯H/H⋯O (22.4%). For (II), the most significant contact percentages are H⋯H (36.1%) followed by C⋯H/H⋯C (31.3%).
Rapid and Accurate Prediction of the Axial Magnetic Anisotropy in Cobalt(II) Complexes Using a Machine-Learning Approach
2023, Inorganic Chemistry

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Short communicationCoordination polymers containing a pyrazole-based ligand and 4,4′-bipyridine as a spacer: enhancing the family of nonzero-dimensional compounds featuring single-ion magnetic behavior

Highlights

Abstract

Graphical abstract

Section snippets

Declaration of Competing Interest

Acknowledgments

Magnetic functionalities in MOFs: From the framework to the pore

Chem. Soc. Rev.

Design of magnetic coordination polymers built from polyoxalamide ligands: A thirty year story

Eur. J. Inorg. Chem.

Crystal engineering and IUCrJ

IUCrJ.

A new quartz-like metal-organic framework constructed from a versatile pyrazole-based spacer

Cryst. Growth Des.

Mononuclear coordination compounds containing a pyrazole-based ligand: Syntheses, magnetism and acetylcholinesterase inhibition assays

J. Mol. Struct.

Short communication
Coordination polymers containing a pyrazole-based ligand and 4,4′-bipyridine as a spacer: enhancing the family of nonzero-dimensional compounds featuring single-ion magnetic behavior