Magnetic Lanthanide Complexes

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (30 June 2018) | Viewed by 17351

Special Issue Editors


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Guest Editor
Dipartimento di Chimica "U. Schiff", Università degli Studi di Firenze, Via della Lastruccia 3-13, 50019 Sesto Fiorentino, Italy
Interests: magnetic anisotropy; electron paramagnetic resonance; lanthanides; molecular qubits ; molecular magnetism; single molecule magnets; spin dynamics

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Guest Editor
Dipartimento di Chimica "U.Schiff" and UdR INSTM, Università degli Studi di Firenze, Sesto Fiorentino, Italy
Interests: ab initio; DFT; modeling; magnetic clusters

Special Issue Information

Dear Colleagues,

Coordination compounds based on lanthanide ions are the focus of intense research due to their peculiar magnetic properties, which arise as a consequence of their large magnetic moment and large anisotropy. Recent research brought these systems at the forefront of the research interest, thanks to the discovery of magnetic bistability on mononuclear complexes, which might pave the way for the use of these systems as magnetic memory molecular units. At the same time, the discovery that long electron decoherence and short correlation times can be obtained in such systems has suggested their potential use as molecular spin qubits and as candidates for next generation MRI agents. Thanks to major advances in both experimental techniques and theoretical methods past years have witnessed a tremendous advance in our comprehension of several different aspects of the magnetic properties of these systems. These range from accurate calculations of electronic structure and its connections with both static and dynamic magnetic behaviour to a more accurate comprehension of magnetic anisotropy in these systems and the way to engineer it; from observation of magnetically bistable systems at increasingly high temperature to experimentally and theoretically feasible determination of exchange coupling. However, several crucial points are still open. Among them, the fine understanding of the degree of covalence in the lanthanide coordination bond and the role of the electrostatic environment in determining the magnetic properties, as well as the role of vibrations in determining the magnetization dynamics and the experimental identification of the correct relaxation process. We firmly believe the study of these issues will be important topics in the future investigation of magnetic lanthanide compounds.

This Special Issue aims at collecting experimental and theoretical research and review contributions of recent advances in all aspects of magnetic properties of lanthanide complexes and to share this knowledge with a broader audience by means of an open access publication policy. We invite you to contribute papers in the above-mentioned areas and allow your research to impact the next generation trend in this exciting field.

Prof. Dr. Lorenzo Sorace
Prof. Dr. Federico Totti
Guest Editors

Manuscript Submission Information

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Keywords

  • anisotropy
  • exchange coupling
  • covalency
  • modeling
  • slow relaxation

Published Papers (3 papers)

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Research

9 pages, 2035 KiB  
Communication
Exploring High-Symmetry Lanthanide-Functionalized Polyoxopalladates as Building Blocks for Quantum Computing
by José J. Baldoví and Aleksandar Kondinski
Inorganics 2018, 6(4), 101; https://doi.org/10.3390/inorganics6040101 - 21 Sep 2018
Cited by 9 | Viewed by 4291
Abstract
The structural, electronic, and magnetochemical properties of the star-shaped polyoxopalladate [Pd15O10(SeO3)10]10− (POPd) and its lanthanide-functionalized derivatives have been investigated on the basis of density functional theory, followed by a ligand field analysis using the [...] Read more.
The structural, electronic, and magnetochemical properties of the star-shaped polyoxopalladate [Pd15O10(SeO3)10]10− (POPd) and its lanthanide-functionalized derivatives have been investigated on the basis of density functional theory, followed by a ligand field analysis using the Radial Effective Charge (REC) model. Our study predicts that heteroPOPd is a robust cryptand that enforces D5h symmetry around the encapsulated Ln3+ centers. This rigid coordination environment favors an interesting potential magnetic behavior in the Er and Ho derivatives, and the presence of a cavity in the structure suggests an effective insulation of the electronic system from the lattice phonons, which may be of interest for molecular spintronics and quantum computing applications. Full article
(This article belongs to the Special Issue Magnetic Lanthanide Complexes)
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12 pages, 2409 KiB  
Article
Chiral, Heterometallic Lanthanide–Transition Metal Complexes by Design
by Anders Øwre, Morten Vinum, Michal Kern, Joris Van Slageren, Jesper Bendix and Mauro Perfetti
Inorganics 2018, 6(3), 72; https://doi.org/10.3390/inorganics6030072 - 19 Jul 2018
Cited by 7 | Viewed by 5879
Abstract
Achieving control over coordination geometries in lanthanide complexes remains a challenge to the coordination chemist. This is particularly the case in the field of molecule-based magnetism, where barriers for magnetic relaxation processes as well as tunneling pathways are strongly influenced by the lanthanide [...] Read more.
Achieving control over coordination geometries in lanthanide complexes remains a challenge to the coordination chemist. This is particularly the case in the field of molecule-based magnetism, where barriers for magnetic relaxation processes as well as tunneling pathways are strongly influenced by the lanthanide coordination geometry. Addressing the challenge of design of 4f-element coordination environments, the ubiquitous Ln(hfac)3 moieties have been shown to be applicable as Lewis acids coordinating transition metal acetylacetonates facially leading to simple, chiral lanthanide–transition metal heterodinuclear complexes. The broad scope of this approach is illustrated by the synthesis of a range of such complexes LnM: LnM(hfac)32-acac-O,O,O′)3 (Ln = La, Pr, Gd; M = Cr, Fe, Ga), with approximate three-fold symmetry. The complexes have been crystallographically characterized and exhibit polymorphism for some combinations of 4f and 3d metal centers. However, an isostructural set of systems spanning several lanthanides which exhibit spontaneous resolution in the orthorhombic Sohncke space group P212121 is presented here. The electronic structure and ensuing magnetic properties have been studied by EPR spectroscopy and magnetometry. The GdFe, PrFe, and PrCr complexes exhibit ferromagnetic coupling, while GdCr exhibits antiferromagnetic coupling. GdGa exhibits slow relaxation of the magnetization in applied static fields. Full article
(This article belongs to the Special Issue Magnetic Lanthanide Complexes)
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17 pages, 6164 KiB  
Article
Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy
by Stuart K. Langley, Kuduva R. Vignesh, Kerey Holton, Sophie Benjamin, Gary B. Hix, Wasinee Phonsri, Boujemaa Moubaraki, Keith S. Murray and Gopalan Rajaraman
Inorganics 2018, 6(2), 61; https://doi.org/10.3390/inorganics6020061 - 12 Jun 2018
Cited by 17 | Viewed by 6681
Abstract
We report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3 [...] Read more.
We report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3)4(NO3)2](NO3) (2), [DyIII(OPPh3)3Cl3] (3), [DyIII(OPPh3)4Cl2]Cl (4) and [DyIII(OPPh3)4Cl2](FeCl4) (5). These complexes are characterized using single crystal X-ray diffraction, which revealed that each complex has a unique coordination environment around the DyIII ion, which results in varying dynamic magnetic behavior. Ab initio calculations are performed to rationalize the observed magnetic behavior and to understand the effect that the ligand and coordination geometry around the DyIII ion has on the single-molecule magnet (SMM) behavior. In recent years, seven coordinate DyIII complexes possessing pseudo ~D5h symmetry are found to yield attractive blocking temperatures for the development of new SMM complexes. However, here we show that the strength of the donor ligand plays a critical role in determining the effective energy barrier and is not simply dependent on the geometry and the symmetry around the DyIII ion. Seven coordinate molecules possessing pseudo D5h symmetry with strong equatorial ligation and weak axial ligation are found to be inferior, exhibiting no SMM characteristics under zero-field conditions. Thus, this comprehensive study offers insight on improving the blocking temperature of mononuclear SMMs. Full article
(This article belongs to the Special Issue Magnetic Lanthanide Complexes)
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