Special Issue "Molecular Magnetism of Lanthanides Complexes and Networks"

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

Deadline for manuscript submissions: closed (15 June 2017)

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Guest Editor
Dr. Kevin Bernot

Institut des Sciences Chimiques de Rennes (ISCR), INSA-Rennes, 20 av. des buttes de Coësmes, 35708 Rennes, France
Website | E-Mail
Phone: +33 (0)2 23 23 84 34
Interests: lanthanides; coordination chemistry; molecular magnetism; luminescence; single-molecule magnets; single-chain magnets; radical ligands; metal-organic frameworks; multifunctional materials; surfaces

Special Issue Information

Dear Colleagues,

In the last ten years, a fresh air has been blowing in the field of Molecular Magnetism with the re-introduction of lanthanides ions as spin carriers in magnetic molecules. Their strong magnetic moment and huge magnetic anisotropy are strong assets that have enabled breakthroughs in magnetic blocking temperature and related phenomena. The chemical versatility of these ions is also a crucial benefit, as easy substitution among the lanthanides series can either afford isotropic, anisotropic or solid-solutions of magnetic molecules. In a similar way, their well-known luminescent properties have been identified as key features to rationalize SMMs behavior and theoretical approaches have made a great deal of progress.

Moreover, aside from their use as building blocks for high performance SMMs, lanthanides ions permitted the design of unique magnetic compounds that found numerous other applications that ranges from molecular magnetic coolers to spintronics devices, qubits and more generally multifunctional materials.

This Special Issue of Magnetochemistry is a key forum to publish your latest research in lanthanide-based compounds, and, more specifically, in the fields listed below.

Dr. Kevin Bernot
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Magnetochemistry is an international peer-reviewed open access quarterly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 350 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Lanthanide-based magnetic molecules (SMMs, SCMs, extended networks and MOFs, organometallics, polyoxometalates, hetero-spin systems,...)
  • Lanthanide-based spintronics and qubits
  • Lanthanide-based magnetic coolers
  • Lanthanide-based magnetic molecules on surfaces
  • Lanthanide-based multifunctional magnetic materials
  • Computational approaches of Lanthanide-based molecules
  • Characterization techniques of Lanthanide-based magnetic materials

Published Papers (8 papers)

View options order results:
result details:
Displaying articles 1-8
Export citation of selected articles as:

Editorial

Jump to: Research, Review

Open AccessEditorial Molecular Magnetism of Lanthanides Complexes and Networks
Magnetochemistry 2017, 3(3), 26; https://doi.org/10.3390/magnetochemistry3030026
Received: 24 July 2017 / Revised: 29 July 2017 / Accepted: 30 July 2017 / Published: 2 August 2017
PDF Full-text (166 KB) | HTML Full-text | XML Full-text
Abstract
Lanthanides ions allows for the design of remarkable magnetic compounds with unique magnetic properties.[...] Full article

Research

Jump to: Editorial, Review

Open AccessArticle Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies
Magnetochemistry 2017, 3(1), 5; https://doi.org/10.3390/magnetochemistry3010005
Received: 21 December 2016 / Revised: 13 January 2017 / Accepted: 16 January 2017 / Published: 26 January 2017
Cited by 12 | PDF Full-text (3243 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The 1:1 reactions between hydrated lanthanide(III) nitrates and triethanolamine (teaH3) in MeOH, in the absence of external bases, have provided access to the dinuclear complexes [Ln2(NO3)4(teaH2)2] (Ln = Pr, 1; [...] Read more.
The 1:1 reactions between hydrated lanthanide(III) nitrates and triethanolamine (teaH3) in MeOH, in the absence of external bases, have provided access to the dinuclear complexes [Ln2(NO3)4(teaH2)2] (Ln = Pr, 1; Ln = Gd, 2; Ln = Tb, 3; Ln = Dy, 4; Ln = Ho, 5) containing the singly deprotonated form of the ligand. Use of excess of the ligand in the same solvent gives mononuclear complexes containing the neutral ligand and the representative compound [Pr(NO3)(teaH3)2](NO3)2 (6) was characterized. The structures of the isomorphous complexes 1∙2MeOH, 2∙2MeOH and 4∙2MeOH were solved by single-crystal X-ray crystallography; the other two dinuclear complexes are proposed to be isostructural with 1, 2 and 4 based on elemental analyses, IR spectra and powder XRD patterns. The IR spectra of 16 are discussed in terms of structural features of the complexes. The two LnIII atoms in centrosymmetric 1∙2MeOH, 2∙2MeOH and 4∙2MeOH are doubly bridged by the deprotonated oxygen atoms of the two η11122 teaH2 ligands. The teaH2 nitrogen atom and six terminal oxygen atoms (two from the neutral hydroxyl groups of teaH2 and four from two slightly anisobidentate chelating nitrato groups) complete 9-coordination at each 4f-metal center. The coordination geometries of the metal ions are spherical-relaxed capped cubic (1∙2MeOH), Johnson tricapped trigonal prismatic (2∙2MeOH) and spherical capped square antiprismatic (4·2MeOH). O–H∙∙∙O H bonds create chains parallel to the a axis. The cation of 6 has crystallographic two fold symmetry and the rotation axis passes through the PrIII atom, the nitrogen atom of the coordinated nitrato group and the non-coordinated oxygen atom of the nitrato ligand. The metal ion is bound to the two η1111 teaH3 ligands and to one bidentate chelating nitrato group. The 10-coordinate PrIII atom has a sphenocoronal coordination geometry. Several H bonds are responsible for the formation of a 3D architecture in the crystal structure of 6. Complexes 16 are new members of a small family of homometallic LnIII complexes containing various forms of triethanolamine as ligands. Dc magnetic susceptibility studies in the 2–300 K range reveal the presence of a weak to moderate intramolecular antiferromagnetic exchange interaction (J = −0.30(2) cm−1 based on the spin Hamiltonian H ^ = - J ( S ^ Gd 1 S ^ Gd 1 ) ) for 2 and probably weak antiferromagnetic exchange interactions within the molecules of 35. The antiferromagnetic GdIII∙∙∙GdIII interaction in 2 is discussed in terms of known magnetostructural correlations for complexes possessing the {Gd22-OR)2}4+ core. Ac magnetic susceptibility measurements in zero dc field for 35 do not show frequency dependent out-of-phase signals; this experimental fact is discussed and rationalized for complex 4 in terms of the magnetic anisotropy axis for each DyIII center and the oblate electron density of the metal ion. Full article
Figures

Graphical abstract

Open AccessFeature PaperArticle Slow Magnetic Relaxation in Chiral Helicene-Based Coordination Complex of Dysprosium
Magnetochemistry 2017, 3(1), 2; https://doi.org/10.3390/magnetochemistry3010002
Received: 9 November 2016 / Revised: 9 December 2016 / Accepted: 13 December 2016 / Published: 23 December 2016
Cited by 7 | PDF Full-text (4041 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The complex [Dy(L)(tta)3] with L the chiral 3-(2-pyridyl)-4-aza[6]-helicene ligand (tta = 2-thenoyltrifluoroaacetonate) has been synthesized in its racemic form and structurally and magnetically characterized. [Dy(L)(tta)3] behaves as a single molecule magnet in its crystalline [...] Read more.
The complex [Dy(L)(tta)3] with L the chiral 3-(2-pyridyl)-4-aza[6]-helicene ligand (tta = 2-thenoyltrifluoroaacetonate) has been synthesized in its racemic form and structurally and magnetically characterized. [Dy(L)(tta)3] behaves as a single molecule magnet in its crystalline phase with the opening of a hysteresis loop at 0.50 K. These magnetic properties were interpreted with ab initio calculations. Full article
Figures

Graphical abstract

Open AccessArticle Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions
Magnetochemistry 2017, 3(1), 1; https://doi.org/10.3390/magnetochemistry3010001
Received: 7 November 2016 / Revised: 7 December 2016 / Accepted: 13 December 2016 / Published: 22 December 2016
Cited by 3 | PDF Full-text (6528 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The syntheses and characterization of four new hybrid coordination networks based on lanthanide ions (Ln = Nd, Sm) and 1,3-carboxymethylimidazolium (L) salt in the presence of oxalic acid (H2ox) are reported. The influence of the synthesis parameters, such as [...] Read more.
The syntheses and characterization of four new hybrid coordination networks based on lanthanide ions (Ln = Nd, Sm) and 1,3-carboxymethylimidazolium (L) salt in the presence of oxalic acid (H2ox) are reported. The influence of the synthesis parameters, such as the nature of the lanthanide ion (Nd3+ or Sm3+), the nature of the imidazolium source (chloride [H2L][Cl] or zwitterionic [HL] form) and the presence or not of oxalic acid (H2ox), is discussed. In the presence of oxalic acid, the samarium salt gives only one compound [Sm(L)(ox)(H2O)]·H2O, whatever the nature of the imidazolium ligand, while the neodymium salt leads to three different compounds, [Nd(L)(ox)(H2O)]·H2O, [Nd(L)(ox)0.5(H2O)2][Cl] or [Nd2(L)2(ox)(NO3)(H2O)3][NO3], depending on the imidazolium ligand. In the absence of oxalic acid, gels are obtained, except for the reaction between the neodymium salt and [H2L][Cl], which leads to [Nd(L)(ox)(H2O)]·H2O. All compounds crystallized and their structures were determined by single crystal diffraction. The description of these new phases was consistently supported by ancillary techniques, such as powder X-ray diffraction, thermal analyses and UV-visible-near infrared spectroscopy. The luminescent and magnetic properties of the three pure compounds [Sm(L)(ox)(H2O)]·H2O, [Nd(L)(ox)(H2O)]·H2O and [Nd2(L)2(ox)(NO3)(H2O)3][NO3] were also studied. Full article
Figures

Graphical abstract

Open AccessArticle Hybrid Molecular Compound Exhibiting Slow Magnetic Relaxation and Electrical Conductivity
Magnetochemistry 2016, 2(4), 44; https://doi.org/10.3390/magnetochemistry2040044
Received: 27 September 2016 / Revised: 28 November 2016 / Accepted: 30 November 2016 / Published: 9 December 2016
Cited by 5 | PDF Full-text (3940 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Electrochemical oxidation of a solution containing KDy(hfac)4 (hfac, hexafluoroacetyacetone) and Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) afforded a hybrid material formulated as [β′-(BEDT-TTF)2Dy(CF3COO)4∙MeCN]n. The complex crystallizes in the triclinic space group P1¯. The before mentioned [...] Read more.
Electrochemical oxidation of a solution containing KDy(hfac)4 (hfac, hexafluoroacetyacetone) and Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) afforded a hybrid material formulated as [β′-(BEDT-TTF)2Dy(CF3COO)4∙MeCN]n. The complex crystallizes in the triclinic space group P 1 ¯ . The before mentioned complex has a chain structure containing 4f ions bridged by mono-anion CF3COO ligand, and acts as single-molecule magnet (SMM) at low temperature. The conducting layer was composed of partially oxidized BEDT-TTF molecules in β′ type arrangement. The presence of radical cation and its charge ordering was assigned on the basis of optical spectra. Electrical resistivity measurements revealed semiconducting behaviour (conductivity at room temperature of 1.1 × 10−3 S·cm−1, activation energy of 158.5 meV) at ambient pressure. Full article
Figures

Graphical abstract

Open AccessArticle Slow Magnetic Relaxation of Lanthanide(III) Complexes with a Helical Ligand
Magnetochemistry 2016, 2(4), 43; https://doi.org/10.3390/magnetochemistry2040043
Received: 31 October 2016 / Revised: 28 November 2016 / Accepted: 30 November 2016 / Published: 8 December 2016
Cited by 9 | PDF Full-text (4016 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Isostructural Ln(III) mononuclear complexes [Ln(NO3)2L]PF6·MeCN (Ln = Nd, Tb, or Dy; L denotes a helical hexa-dentate ligand) were synthesized, and their slow magnetic relaxation behavior was investigated. In these complexes, oblate-type Ln(III) ions are located in an [...] Read more.
Isostructural Ln(III) mononuclear complexes [Ln(NO3)2L]PF6·MeCN (Ln = Nd, Tb, or Dy; L denotes a helical hexa-dentate ligand) were synthesized, and their slow magnetic relaxation behavior was investigated. In these complexes, oblate-type Ln(III) ions are located in an axially stressed ligand field with two nitrate anions, and can exhibit single-molecule magnet (SMM) behavior. Field-induced SMM behavior was observed for Nd(III) and Dy(III) complexes under an applied bias DC field of 1000 Oe. Full article
Figures

Graphical abstract

Open AccessArticle Magneto-Luminescence Correlation in the Textbook Dysprosium(III) Nitrate Single-Ion Magnet
Magnetochemistry 2016, 2(4), 41; https://doi.org/10.3390/magnetochemistry2040041
Received: 11 October 2016 / Revised: 10 November 2016 / Accepted: 12 November 2016 / Published: 18 November 2016
Cited by 14 | PDF Full-text (2111 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Multifunctional Single-Molecule Magnets (SMMs) or Single-Ion Magnets (SIMs) are intriguing molecule-based materials presenting an association of the slow magnetic relaxation with other physical properties. In this article, we present an example of a very simple molecule based on Dy3+ ion exhibiting a [...] Read more.
Multifunctional Single-Molecule Magnets (SMMs) or Single-Ion Magnets (SIMs) are intriguing molecule-based materials presenting an association of the slow magnetic relaxation with other physical properties. In this article, we present an example of a very simple molecule based on Dy3+ ion exhibiting a field induced SIM property and a characteristic Dy3+ based emission. The [Dy(NO3)3(H2O)4]·2H2O (1) complex is characterized by the means of single crystal X-Ray diffraction and their magnetic and photo-luminescent properties are investigated. We demonstrate here that it is possible to correlate the magnetic and luminescent properties and to obtain the Orbach barrier from the low temperature emission spectra, which is often difficult to properly extract from the magnetic measurements, especially in the case of field induced SIMs. Full article
Figures

Graphical abstract

Review

Jump to: Editorial, Research

Open AccessReview Perspectives on Neutron Scattering in Lanthanide-Based Single-Molecule Magnets and a Case Study of the Tb2(μ-N2) System
Magnetochemistry 2016, 2(4), 45; https://doi.org/10.3390/magnetochemistry2040045
Received: 8 November 2016 / Revised: 24 November 2016 / Accepted: 25 November 2016 / Published: 14 December 2016
Cited by 9 | PDF Full-text (6161 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Single-molecule magnets (SMMs) based on lanthanide ions display the largest known blocking temperatures and are the best candidates for molecular magnetic devices. Understanding their physical properties is a paramount task for the further development of the field. In particular, for the poly-nuclear variety [...] Read more.
Single-molecule magnets (SMMs) based on lanthanide ions display the largest known blocking temperatures and are the best candidates for molecular magnetic devices. Understanding their physical properties is a paramount task for the further development of the field. In particular, for the poly-nuclear variety of lanthanide SMMs, a proper understanding of the magnetic exchange interaction is crucial. We discuss the strengths and weaknesses of the neutron scattering technique in the study of these materials and particularly for the determination of exchange. We illustrate these points by presenting the results of a comprehensive inelastic neutron scattering study aimed at a radical-bridged diterbium(III) cluster, Tb2(μ-N23−), which exhibits the largest blocking temperature for a poly-nuclear SMM. Results on the YIII analogue Y2(μ-N23−) and the parent compound Tb2(μ-N22−) (showing no SMM features) are also reported. The results on the parent compound include the first direct determination of the lanthanide-lanthanide exchange interaction in a molecular cluster based on inelastic neutron scattering. In the SMM compound, the resulting physical picture remains incomplete due to the difficulties inherent to the problem. Full article
Figures

Figure 1

Magnetochemistry EISSN 2312-7481 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top