From Magnetic Anisotropy to Molecular Magnets: Theory and Experiments

A special issue of Magnetochemistry (ISSN 2312-7481).

Deadline for manuscript submissions: closed (30 April 2021) | Viewed by 15582

Special Issue Editor


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Guest Editor
Laboratoire de Chimie de Coordination (LCC), French National Centre for Scientific Research, 31077 Toulouse, France
Interests: molecule-based magnetic architectures; molecular nanomagnets

Special Issue Information

Dear Colleagues,

Magnetic anisotropy is central to the characteristics of magnetic materials. Over the past 15 years or so, it has been the driving force behind work in the field of molecular magnetism. The combined efforts of chemists, physicists, and theorists now enable us to manipulate it deliberately through coordination chemistry, and this control has led to dazzling progress in the performance of nanomagnets, SMM, and SCM. Traditional magnets are not to be outdone, whether they are molecular materials or inorganic nanoparticles.

The aim of this Special Issue is to provide an overview of the latest knowledge, approaches, and developments related to magnetic anisotropy, and the resulting materials and properties. The idea is to provide a newcomer to the field with easy access to the various facets of this property, both from a theoretical and experimental point of view. To this end, we are seeking tutorials and research papers on magnetic anisotropy in coordination compounds and the materials derived from them: SIM, SMM, SCM, nanoparticles, traditional magnets, etc.

Dr. Jean-Pascal Sutter
Guest Editor

Manuscript Submission Information

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Keywords

  • magnetic anisotropy
  • single-molecule magnet
  • single-chain magnet
  • nanoparticle
  • magnet
  • molecular magnetism

Published Papers (5 papers)

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Research

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14 pages, 1418 KiB  
Article
Crystal Structure and Magnetic Properties of Peacock–Weakley Type Polyoxometalates Na9[Ln(W5O18)2] (Ln = Tm, Yb): Rare Example of Tm(III) SMM
by Oleksandra Yu. Mariichak, Sandra Kaabel, Yevgen A. Karpichev, Georgiy M. Rozantsev, Serhii V. Radio, Céline Pichon, Hélène Bolvin and Jean-Pascal Sutter
Magnetochemistry 2020, 6(4), 53; https://doi.org/10.3390/magnetochemistry6040053 - 21 Oct 2020
Cited by 7 | Viewed by 3901
Abstract
We report Peacock–Weakley complexes, Na9[Ln(W5O18)2]∙35H2O, formed with Tm(III), 1, and Yb(III), 2. Their syntheses, physico-chemical characterizations, crystal structures, and magnetic properties are described. Ab initio calculations are also reported. These polyoxometalate [...] Read more.
We report Peacock–Weakley complexes, Na9[Ln(W5O18)2]∙35H2O, formed with Tm(III), 1, and Yb(III), 2. Their syntheses, physico-chemical characterizations, crystal structures, and magnetic properties are described. Ab initio calculations are also reported. These polyoxometalate (POM) complexes were obtained using original synthetic conditions where acidification was performed with a stoichiometric amount of nitric acid to an acidity of Z = ν(H+)/ν(WO42–) = 8/10 = 0.80. Both the Tm(III) and Yb(III) derivatives were found to exhibit field-induced slow relaxation of their magnetization likely controlled by Raman and Orbach relaxation processes. 1 is a rare example of a Tm(III)-based single-molecule magnet (SMM) and is a consequence of the oblate tetragonal anti-prismatic symmetry of the coordination sphere. Full article
(This article belongs to the Special Issue From Magnetic Anisotropy to Molecular Magnets: Theory and Experiments)
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11 pages, 4787 KiB  
Article
Nitronyl Nitroxide Biradical-Based Binuclear Lanthanide Complexes: Structure and Magnetic Properties
by Lu Xi, Jing Han, Xiaohui Huang and Licun Li
Magnetochemistry 2020, 6(4), 48; https://doi.org/10.3390/magnetochemistry6040048 - 3 Oct 2020
Cited by 5 | Viewed by 2779
Abstract
Employing a new nitronyl nitroxide biradical NITPhPzbis(NITPhPzbis = 5-(1-pyrazolyl)-1,3-bis(1’-oxyl-3’-oxido-4’,4’,5’,5’-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene), a series of 2p-4f complexes [Ln2(hfac)6(H2O)(NITPhPzbis)] (LnIII = Gd1, Tb2, Dy3; hfac = hexafluoroacetylacetonate) were successfully [...] Read more.
Employing a new nitronyl nitroxide biradical NITPhPzbis(NITPhPzbis = 5-(1-pyrazolyl)-1,3-bis(1’-oxyl-3’-oxido-4’,4’,5’,5’-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene), a series of 2p-4f complexes [Ln2(hfac)6(H2O)(NITPhPzbis)] (LnIII = Gd1, Tb2, Dy3; hfac = hexafluoroacetylacetonate) were successfully synthesized. In complexes 13, the designed biradical NITPhPzbis coordinates with two LnIII ions in chelating and bridging modes to form a four-spin binuclear structure. Direct-current magnetic study of Gd analogue indicates that ferromagnetic exchange exists between the Gd ion and the radical while antiferromagnetic coupling dominates between two mono-radicals. Dynamic magnetic data show that the χ” signals of complex 3 exhibit frequency dependence under zero field, demonstrating slow magnetic relaxation behavior in complex 3. And the estimated values of Ueff and τ0 are about 8.4 K and 9.1 × 10−8 s, respectively. Full article
(This article belongs to the Special Issue From Magnetic Anisotropy to Molecular Magnets: Theory and Experiments)
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13 pages, 3921 KiB  
Article
Redox Modulation of Field-Induced Tetrathiafulvalene-Based Single-Molecule Magnets of Dysprosium
by Siham Tiaouinine, Jessica Flores Gonzalez, Vincent Montigaud, Carlo Andrea Mattei, Vincent Dorcet, Lakhmici Kaboub, Vladimir Cherkasov, Olivier Cador, Boris Le Guennic, Lahcène Ouahab, Viacheslav Kuropatov and Fabrice Pointillart
Magnetochemistry 2020, 6(3), 34; https://doi.org/10.3390/magnetochemistry6030034 - 19 Aug 2020
Cited by 7 | Viewed by 2281
Abstract
The complexes [Dy2(tta)6(H2SQ)] (Dy-H2SQ) and [Dy2(tta)6(Q)]·2CH2Cl2 (Dy-Q) (tta = 2-thenoyltrifluoroacetonate) were obtained from the coordination reaction of the Dy(tta)3·2H [...] Read more.
The complexes [Dy2(tta)6(H2SQ)] (Dy-H2SQ) and [Dy2(tta)6(Q)]·2CH2Cl2 (Dy-Q) (tta = 2-thenoyltrifluoroacetonate) were obtained from the coordination reaction of the Dy(tta)3·2H2O units with the 2,2′-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate ligand (H2SQ) and its oxidized form 2,2′-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q). The chemical oxidation of H2SQ in Q induced an increase in the coordination number from 7 to 8 around the DyIII ions and by consequence a modulation of the field-induced Single-Molecule Magnet behavior. Computational results rationalized the magnetic properties of each of the dinuclear complexes. Full article
(This article belongs to the Special Issue From Magnetic Anisotropy to Molecular Magnets: Theory and Experiments)
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Review

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18 pages, 2918 KiB  
Review
Polarized Neutron Diffraction: An Excellent Tool to Evidence the Magnetic Anisotropy—Structural Relationships in Molecules
by Dominique Luneau and Béatrice Gillon
Magnetochemistry 2021, 7(12), 158; https://doi.org/10.3390/magnetochemistry7120158 - 6 Dec 2021
Cited by 5 | Viewed by 2513
Abstract
This publication reviews recent advances in polarized neutron diffraction (PND) studies of magnetic anisotropy in coordination compounds comprising d or f elements and having different nuclearities. All these studies illustrate the extent to which PND can provide precise and direct information on the [...] Read more.
This publication reviews recent advances in polarized neutron diffraction (PND) studies of magnetic anisotropy in coordination compounds comprising d or f elements and having different nuclearities. All these studies illustrate the extent to which PND can provide precise and direct information on the relationship between molecular structure and the shape and axes of magnetic anisotropy of the individual metal sites. It makes this experimental technique (PND) an excellent tool to help in the design of molecular-based magnets and especially single-molecule magnets for which strong uniaxial magnetic anisotropy is required. Full article
(This article belongs to the Special Issue From Magnetic Anisotropy to Molecular Magnets: Theory and Experiments)
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29 pages, 10384 KiB  
Review
High-Coordinate Mononuclear Ln(III) Complexes: Synthetic Strategies and Magnetic Properties
by Joydev Acharya, Pankaj Kalita and Vadapalli Chandrasekhar
Magnetochemistry 2021, 7(1), 1; https://doi.org/10.3390/magnetochemistry7010001 - 22 Dec 2020
Cited by 11 | Viewed by 3284
Abstract
Single-molecule magnets involving monometallic 4f complexes have been investigated extensively in last two decades to understand the factors that govern the slow magnetization relaxation behavior in these complexes and to establish a magneto-structural correlation. The prime goal in this direction is to suppress [...] Read more.
Single-molecule magnets involving monometallic 4f complexes have been investigated extensively in last two decades to understand the factors that govern the slow magnetization relaxation behavior in these complexes and to establish a magneto-structural correlation. The prime goal in this direction is to suppress the temperature independent quantum tunneling of magnetization (QTM) effect via fine-tuning the coordination geometry/microenvironment. Among the various coordination geometries that have been pursued, complexes containing high coordination number around Ln(III) are sparse. Herein, we present a summary of the various synthetic strategies that were used for the assembly of 10- and 12-coordinated Ln(III) complexes. The magnetic properties of such complexes are also described. Full article
(This article belongs to the Special Issue From Magnetic Anisotropy to Molecular Magnets: Theory and Experiments)
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