Magnetic Coordination Polymers

A special issue of Magnetochemistry (ISSN 2312-7481). This special issue belongs to the section "Magnetic Materials".

Deadline for manuscript submissions: closed (31 August 2021) | Viewed by 8484

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Laboratory of Inorganic Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta nr. 4-12, Bucharest, Romania
Interests: molecular magnetism; crystal engineering; metallosupramolecular chemistry; homo- and hetero-polynuclear complexes
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Special Issue Information

Coordination polymers with various dimensionalities are of high interest in molecular magnetism. One-dimensional coordination polymers may behave as single-chain magnets or chains of single-molecule magnets; two-dimensional coordination polymers can also exhibit slow relaxation of the magnetization phenomena (layers of single-chain magnets); three-dimensional coordination polymers have been intensively investigated in the search for molecule-based magnets and are very topical, particularly, when magnetic properties are combined with other properties (porosity, luminescence, sensing of various molecules with modulation of the magnetic behavior). Numerous spin-crossover materials are coordination polymers. All these goals stimulate the development of new synthetic approaches leading to a very rich structural variety of homo- and hetero-metallic networks. Consequently, we consider that a Special Issue dedicated to coordination polymers and their relevance in molecular magnetism is welcome.

Prof. Dr. Marius Andruh
Guest Editor

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Keywords

  • Magnetic coordination polymers
  • single-chain magnets
  • single-molecule magnets
  • 3D molecule-based magnets
  • spin-crossover complexes.

Published Papers (3 papers)

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Research

17 pages, 4984 KiB  
Article
Effect of the Alkaline Metal Ion on the Crystal Structure and Magnetic Properties of Heterometallic GdIII-VIV Complexes Based on Cyclobutane-1,1-Dicarboxylate Anions
by Evgeniya S. Bazhina, Alexander A. Korlyukov, Julia K. Voronina, Konstantin A. Babeshkin, Elena A. Ugolkova, Nikolay N. Efimov, Matvey V. Fedin, Mikhail A. Kiskin and Igor L. Eremenko
Magnetochemistry 2021, 7(6), 82; https://doi.org/10.3390/magnetochemistry7060082 - 3 Jun 2021
Cited by 3 | Viewed by 2255
Abstract
A series of heterometallic GdIII-VIV compounds were synthesized by the reaction of VOSO4·3H2O with cyclobutane-1,1-dicarboxylic acid salts M2(cbdc) (M = Na, Rb, Cs). The new compounds were formed by [Gd(VO)2(cbdc)4(H [...] Read more.
A series of heterometallic GdIII-VIV compounds were synthesized by the reaction of VOSO4·3H2O with cyclobutane-1,1-dicarboxylic acid salts M2(cbdc) (M = Na, Rb, Cs). The new compounds were formed by [Gd(VO)2(cbdc)4(H2O)8] trinuclear anionic units that were similar in composition but differed in structure, depending on the nature of the alkali metal cation incorporated in the crystal structure of the compound. In the case of Na+, the {GdV2} units were characterized by identical V···Gd distances and were linked into the 1D-polymeric chain [NaGd(VO)2(cbdc)4(H2O)10]n (1). In the systems with Rb+ and Cs+, the V···Gd distances were different, and the {GdV2} units were linked into the 3D-framework {[RbGd(VO)2(cbdc)4(H2O)10]·2.5H2O}n (2) and the octanuclear molecule {[CsGd(VO)2(cbdc)4(H2O)11]·5H2O}2 (3), respectively. According to dc-magnetic measurements, the VIV and GdIII ions were ferromagnetically coupled in compound 1 (JVGd = 0.163 ± 0.008 cm−1), while in compounds 2 and 3, ferro- and weak antiferromagnetic exchange interactions were observed (JVGd = 0.989 ± 0.028 and −0.089 ± 0.008 cm−1 for 2, 0.656 ± 0.009 and −0.050 ± 0.004 cm−1 for 3). Analysis of the EPR spectra of 1 revealed the presence of weak magnetic anisotropy of GdIII ions (D ~ 0.08 cm−1 and E/D ~ 0.1–0.15). Ac-susceptibility measurements showed an occurrence the field-induced slow relaxation of magnetization in 13. Full article
(This article belongs to the Special Issue Magnetic Coordination Polymers)
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11 pages, 3431 KiB  
Article
Two-Dimensional Nitronyl Nitroxide–Cu Networks Based on Multi-Dentate Nitronyl Nitroxides: Structures and Magnetic Properties
by Hongdao Li, Jiao Lu, Jing Xie, Pei Jing and Licun Li
Magnetochemistry 2021, 7(5), 73; https://doi.org/10.3390/magnetochemistry7050073 - 20 May 2021
Cited by 1 | Viewed by 1976
Abstract
Two multi-dentate nitronyl nitroxide radicals, namely, bisNITPhPy ([5-(4-pyridyl)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)]benzene) and NIT-3Py-5-4Py (2-{3-[5-(4-pyridyl)]pyridyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were assembled with CuII ions to obtain two-dimensional heterospin 2p–3d coordination polymers [Cu7(hfac)14(bisNITPhPy)2]n (1) and [Cu2(hfac)4(NIT-3Py-5-4Py)] [...] Read more.
Two multi-dentate nitronyl nitroxide radicals, namely, bisNITPhPy ([5-(4-pyridyl)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)]benzene) and NIT-3Py-5-4Py (2-{3-[5-(4-pyridyl)]pyridyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were assembled with CuII ions to obtain two-dimensional heterospin 2p–3d coordination polymers [Cu7(hfac)14(bisNITPhPy)2]n (1) and [Cu2(hfac)4(NIT-3Py-5-4Py)]n (2) (hfac: hexafluoroacetylacetonate). In both compounds, the bisNITPhPy and NIT-3Py-5-3Py radicals acted as pentadentate and tetradentate ligands, respectively, to connect with CuII ions, generating a 2D layer structure. The analysis of the magnetic behavior indicated that strong antiferromagnetic coupling and ferromagnetic interaction (J = 17.1 cm−1) coexisted in 1. For 2, there were ferromagnetic couplings between the CuII ion and NO group, as well as the CuII ion and radical via the pyridine ring with J1 = 32.8 and J2 = 2.2 cm−1, respectively. Full article
(This article belongs to the Special Issue Magnetic Coordination Polymers)
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20 pages, 3275 KiB  
Article
X-ray Structure and Magnetic Properties of Heterobimetallic Chains Based on the Use of an Octacyanidodicobalt(III) Complex as Metalloligand
by Maria-Gabriela Alexandru, Diana Visinescu, Sergiu Shova, Abdeslem Bentama, Francesc Lloret, Joan Cano and Miguel Julve
Magnetochemistry 2020, 6(4), 66; https://doi.org/10.3390/magnetochemistry6040066 - 27 Nov 2020
Cited by 4 | Viewed by 3120
Abstract
The assembly of [Co2III(μ-2,5-dpp)(CN)8]2− anions and [MII(CH3OH)2(DMSO)2]2+ cations resulted into the formation of two heterobimetallic 1D coordination polymers of formula [MII(CH3OH)2(DMSO)2 [...] Read more.
The assembly of [Co2III(μ-2,5-dpp)(CN)8]2− anions and [MII(CH3OH)2(DMSO)2]2+ cations resulted into the formation of two heterobimetallic 1D coordination polymers of formula [MII(CH3OH)2(DMSO)2(μ-NC)2Co2III(μ-2,5-dpp)(CN)6]n·4nCH3OH [M = CoII (1)/FeII (2) and 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine. The [Co2III(μ-2,5-dpp)(CN)8]2− metalloligand coordinates the paramagnetic [MII(CH3OH)2(DMSO)2]2+ complex cations, in a bis-monodentate fashion, to give rise to neutral heterobimetallic chains. Cryomagnetic dc (1.9–300 K) and ac (2.0–13 K) magnetic measurements for 1 and 2 show the presence of Co(II)HS (1) and Fe(II)HS (2) ions (HS – high-spin), respectively, with D values of +53.7(5) (1) and −5.1(3) cm−1 (2) and slow magnetic relaxation for 1, this compound being a new example of SIM with transversal magnetic anisotropy. Low-temperature Q-band EPR study of 1 confirms that D value is positive, which reveals the occurrence of a strong asymmetry in the g-tensors and allows a rough estimation of the E/D ratio, whereas 2 is EPR silent. Theoretical calculations by CASSCF/NEVPT2 on 1 and 2 support the results from magnetometry and EPR. The analysis of the ac magnetic measurements of 1 shows that the relaxation of M takes place in the ground state under external magnetic dc fields through dominant Raman and direct spin-phonon processes. Full article
(This article belongs to the Special Issue Magnetic Coordination Polymers)
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