Advances in Lanthanide Coordination Chemistry

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

Deadline for manuscript submissions: closed (30 November 2021) | Viewed by 11424

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Guest Editor
Rennes Institute of Chemical Sciences, University of Rennes 1, 35042 Rennes Cedex, France
Interests: redox-active ligand; lanthanides; coordination chemistry; luminescence; single molecule magnets; spin crossover; chirality; valence tautomerism
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Dear Colleagues,

Lanthanides are fascinating elements due to their specific electronic properties making them suitable candidates for the design of single-molecule/chain magnets, photoluminescent compounds or catalysts having a wide range of potential applications, such as high-density storage, quantum computing, OLEDs, time-resolved imaging, catalysis, etc. The coordination chemistry of lanthanide is central to obtaining the requested electronic properties and to reaching the targeted physical properties. Chemists, physicists, and theorists are working hand in hand to enhance the performances of lanthanide-based materials through the coordination chemistry of lanthanide. For example, coordination of organic chromophore is able to overcome the Laporte forbidden rules allowing the observation of efficient photoluminescence sensitization and exclusive axial coordination of strong Lewis basis ligands, leading to high blocking temperature in SMMs.

This Special Issue of Magnetochemistry aims at publishing a collection of research contributions highlighting the recent achievements in lanthanide coordination chemistry to favor specific ingredients such as crystal field splitting, magnetic anisotropy, etc. for the observation of photoluminescence, slow magnetic relaxation, MOFs, catalytic reaction, etc.

Dr. Fabrice Pointillart
Guest Editor

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Keywords

  • lanthanide coordination and organometallic compounds
  • MOFs
  • molecular magnets
  • single molecule magnets
  • single-chain magnets
  • photoluminescence
  • quantum computing
  • catalysts

Published Papers (4 papers)

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Research

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11 pages, 2197 KiB  
Article
Counterintuitive Single-Molecule Magnet Behaviour in Two Polymorphs of One-Dimensional Compounds Involving Chiral BINOL-Derived Bisphosphate Ligands
by Carlo Andrea Mattei, Bertrand Lefeuvre, Vincent Dorcet, Gilles Argouarch, Olivier Cador, Claudia Lalli and Fabrice Pointillart
Magnetochemistry 2021, 7(11), 150; https://doi.org/10.3390/magnetochemistry7110150 - 16 Nov 2021
Cited by 3 | Viewed by 2412
Abstract
The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the [8′-(Diphenoxylphosphinyl)[1,1′-binaphthalen]-8-yl]diphenoxylphosphine oxide ligand (L) followed by a crystallisation in a 1:3 CH2Cl2:n-hexane solvent mixture led to [...] Read more.
The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the [8′-(Diphenoxylphosphinyl)[1,1′-binaphthalen]-8-yl]diphenoxylphosphine oxide ligand (L) followed by a crystallisation in a 1:3 CH2Cl2:n-hexane solvent mixture led to the isolation of a new polymorph of formula [(Dy(hfac)3((S)-L))3]n (1). The X-ray structure on single crystal of 1 revealed the formation of a mono-dimensional coordination polymer with three crystallographically independent DyIII centres, which crystallised in the polar chiral P21 space group. Ac magnetic measurements highlighted single-molecule magnet behaviour under both zero and 1000 Oe applied magnetic field with magnetic relaxation through quantum tunneling of the magnetisation (QTM, zero field only) and Raman processes. Despite the three crystallographically independent DyIII centres adopting a distorted D4d coordination environment, a single slow magnetic relaxation contribution was observed at a slower rate than its previously studied [(Dy(hfac)3((S)-L))]n (2) polymorph. Full article
(This article belongs to the Special Issue Advances in Lanthanide Coordination Chemistry)
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12 pages, 5136 KiB  
Article
Low-Coordinate Dinuclear Dysprosium(III) Single Molecule Magnets Utilizing LiCl as Bridging Moieties and Tris(amido)amine as Blocking Ligands
by Maria Brzozowska, Gabriela Handzlik, Mikolaj Zychowicz and Dawid Pinkowicz
Magnetochemistry 2021, 7(9), 125; https://doi.org/10.3390/magnetochemistry7090125 - 11 Sep 2021
Cited by 4 | Viewed by 1912
Abstract
A low-coordinate dinuclear dysprosium complex {[Dy(N3N)(THF)][LiCl(THF)]}2 (Dy2) with a double bridging ‘LiCl’ moiety and tris(amido)amine (N3N)3− anions as a blocking ligand is synthesized and characterized structurally and magnetically. Thanks to the use of the [...] Read more.
A low-coordinate dinuclear dysprosium complex {[Dy(N3N)(THF)][LiCl(THF)]}2 (Dy2) with a double bridging ‘LiCl’ moiety and tris(amido)amine (N3N)3− anions as a blocking ligand is synthesized and characterized structurally and magnetically. Thanks to the use of the chelating blocking ligand (N3N)3− equipped with large steric –SiMe3 groups, the coordination sphere of both DyIII ions is restricted to only six donor atoms. The three amido nitrogen atoms determine the orientation of the easy magnetization axes of both DyIII centers. Consequently, Dy2 shows slow magnetic relaxation typical for single molecule magnets (SMMs). However, the effective energy barrier for magnetization reversal determined from the AC magnetic susceptibility measurements is much lower than the separation between the ground and the first excited Kramers doublet based on the CASSCF ab initio calculations. In order to better understand the possible influence of the anticipated intramolecular magnetic interactions in this dinuclear molecule, its GdIII-analog {[Gd(N3N)(THF)][LiCl(THF)]}2 (Gd2) is also synthesized and studied magnetically. Detailed magnetic measurements reveal very weak antiferromagnetic interactions in Gd2. This in turn suggests similar antiferromagnetic interactions in Dy2, which might be responsible for its peculiar SMM behavior and the absence of the magnetic hysteresis loop. Full article
(This article belongs to the Special Issue Advances in Lanthanide Coordination Chemistry)
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20 pages, 3744 KiB  
Article
Near-Infrared Emissive Cyanido-Bridged {YbFe2} Molecular Nanomagnets Sensitive to the Nitrile Solvents of Crystallization
by Michal Liberka, Kseniia Boidachenko, Jakub J. Zakrzewski, Mikolaj Zychowicz, Junhao Wang, Shin-ichi Ohkoshi and Szymon Chorazy
Magnetochemistry 2021, 7(6), 79; https://doi.org/10.3390/magnetochemistry7060079 - 2 Jun 2021
Cited by 9 | Viewed by 2939
Abstract
One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF [...] Read more.
One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF3SO3)3·solv (solv = 2MeCN, 1·MeCN; 2AcrCN, 1·AcrCN; 2PrCN, 1·PrCN; 2MalCN·1MeOH; 1·MalCN; MeCN = acetonitrile, AcrCN = acrylonitrile, PrCN = propionitrile, MalCN = malononitrile). They are based on paramagnetic YbIII centers coordinating diamagnetic [FeII(phen)2(CN)2] metalloligands but differ in the nitrile solvents of crystallization. They exhibit a field-induced slow magnetic relaxation dominated by a Raman process, without an Orbach relaxation as indicated by AC magnetic data and the ab initio calculations. The Raman relaxation is solvent-dependent as represented by the power “n” of the BRamanTn contribution varying from 3.07(1), to 2.61(1), 2.37(1), and 1.68(4) for 1·MeCN, 1·PrCN, 1·AcrCN, and 1·MalCN, respectively, while the BRaman parameter adopts the opposite trend. This was correlated with the variation of phonon modes schemes, including the number of available vibrational modes and their energies, dependent on the increasing complexity of the applied nitrile. 1·MeCN and 1·MalCN show the additional T-independent relaxation assignable to dipole-dipole interactions as confirmed by its suppression in 1·AcrCN and 1·PrCN revealing longer Yb–Yb distances and the disappearance in the LuIII-diluted 1·MeCN@Lu. All compounds exhibit YbIII–centered near-infrared photoluminescence sensitized by organic ligands. Full article
(This article belongs to the Special Issue Advances in Lanthanide Coordination Chemistry)
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Review

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12 pages, 3540 KiB  
Review
Recent Advances in the Catalytic Applications of Lanthanide-Oxo Clusters
by Weiming Huang, Qingxin Liu, Wanmin Chen, Min Feng and Zhiping Zheng
Magnetochemistry 2021, 7(12), 161; https://doi.org/10.3390/magnetochemistry7120161 - 20 Dec 2021
Cited by 11 | Viewed by 3318
Abstract
Lanthanide-oxo/hydroxo clusters (LOCs) in this mini-review refer to polynuclear complexes featuring a polyhedral metal-oxo/hydroxo cluster core of lanthanide ions exclusively or with coexisting 3d metal ions. We summarize herein the recent works using this unique family of cluster complexes for catalysis; this [...] Read more.
Lanthanide-oxo/hydroxo clusters (LOCs) in this mini-review refer to polynuclear complexes featuring a polyhedral metal-oxo/hydroxo cluster core of lanthanide ions exclusively or with coexisting 3d metal ions. We summarize herein the recent works using this unique family of cluster complexes for catalysis; this aspect of research stands in stark contrast to their extensively studied synthetic and structural chemistry as well as the much-researched magnetic properties. Following a brief introduction of the synthetic strategies for these clusters, pertinent results from available literature reports are surveyed and discussed according to the types of catalyzed reactions. Particular attention was paid to the selection of a cluster catalyst for a specific type of reactions as well as the corresponding reaction mechanism. To the end, the advantages and challenges in utilizing LOCs as multifunctional catalysts are summarized, and possible future research directions are proposed. Full article
(This article belongs to the Special Issue Advances in Lanthanide Coordination Chemistry)
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