Special Issue "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)

Special Issue Editors

Guest Editor
Prof. Dr. Lorenzo Sorace

Dipartimento di Chimica "U. Schiff", Università degli Studi di Firenze, Via della Lastruccia 3-13 50019 Sesto Fiorentino, Italy
Website | E-Mail
Interests: magnetic anisotropy; electron paramagnetic resonance; lanthanides; molecular qubits
Guest Editor
Prof. Dr. Federico Totti

Dipartimento di Chimica "U.Schiff" and UdR INSTM, Università degli Studi di Firenze, Sesto Fiorentino, Italy
Website | E-Mail
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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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. Inorganics 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 550 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

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

Published Papers (2 papers)

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Research

Open AccessArticle Chiral, Heterometallic Lanthanide–Transition Metal Complexes by Design
Received: 15 June 2018 / Revised: 12 July 2018 / Accepted: 17 July 2018 / Published: 19 July 2018
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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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Graphical abstract

Open AccessArticle Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy
Received: 1 May 2018 / Revised: 8 June 2018 / Accepted: 9 June 2018 / Published: 12 June 2018
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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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Graphical abstract

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