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Inorganics
Special Issues
Lanthanide Single-Molecule Magnets
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Lanthanide Single-Molecule Magnets

A special issue of Inorganics (ISSN 2304-6740).

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 15131

Special Issue Editor

Dr. Akseli Mansikkamäki

E-Mail Website
Guest Editor
NMR Research Unit, University of Oulu, P.O. Box 8000, FI-90014 Oulu, Finland
Interests: molecular magnetism; quantum chemistry; theoretical chemistry; organometallic chemistry; main-group chemistry; actinide chemistry; spin dynamics; paramagnetic NMR; pseudospin Hamiltonians

Special Issue Information

Dear Colleagues,

Single-molecule magnets (SMMs) are molecular compounds capable of retaining a specific direction of magnetization in the absence of external magnetic fields. They have possible applications as molecular-scale data storage devices, quantum bits in quantum computing, and as possible microscopic components of spintronic devices. Most of the recent milestones in the drive toward SMMs capable of functioning at ambient temperatures can be attributed to coordination complexes of lanthanide ions. The discovery of a dysprosium metallocene SMM functioning at liquid-nitrogen temperature in 2018 sets the current state-of-the-art in the field. Since then, many advances have been made in synthetic approaches, characterization methods, and theoretical models, and new high-temperature SMMs will most likely emerge in the future. This Special Issue aims to collect research and review contributions focusing on the current efforts toward lanthanide SMMs with higher operational temperatures and improved magnetic functionality. An important feature of SMM research is the synergistic relationship between practical synthetic work, experimental characterization, and quantum-chemical calculations; thus, we invite you to contribute your research or review articles focusing on any aspect of the research on lanthanide SMMs.

Dr. Akseli Mansikkamäki
Guest Editor

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Keywords

  • Lanthanides
  • Single-molecule magnets
  • Coordination chemistry
  • Organometallic chemistry
  • Molecular magnetism
  • Magnetochemistry
  • Magnetic characterization
  • Magnetic anisotropy
  • Spin-lattice relaxation
  • Molecular spintronics
  • Multifunctional materials
  • Exchange interaction

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Published Papers (5 papers)

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Research

14 pages, 4111 KiB  
Article
Cyano-Bridged Dy(III) and Ho(III) Complexes with Square-Wave Structure of the Chains
by Valentina D. Sasnovskaya, Leokadiya V. Zorina, Sergey V. Simonov, Artem D. Talantsev and Eduard B. Yagubskii
Inorganics 2022, 10(4), 41; https://doi.org/10.3390/inorganics10040041 - 29 Mar 2022
Viewed by 2508
Abstract
Four new cyano-bridged DyIII-CrIII, DyIII-FeIII, HoIII-CrIII and HoIII-FeIII bimetallic coordination polymers were synthesized by the reaction of [Ln(H2dapsc)(H2O)4](NO3)3 (Ln = [...] Read more.
Four new cyano-bridged DyIII-CrIII, DyIII-FeIII, HoIII-CrIII and HoIII-FeIII bimetallic coordination polymers were synthesized by the reaction of [Ln(H2dapsc)(H2O)4](NO3)3 (Ln = Dy, Ho); H2dapsc = 2,6-diacetylpyridinebis(semicarbazone)) with K3[M(CN)6] (M = Cr, Fe) in H2O, resulting in the substitution of two water molecules in the coordination sphere of rare earth by paramagnetic tricharged hexacyanides of Fe and Cr. The complexes are isostructural and consist of alternating [Ln(H2dapsc)(H2O)2]3+ and [M(CN)6]3− units linked by bridges of two cis-cyano ligands of the anion to form square-wave chains. The ac magnetic measurements revealed that the DyCr and DyFe complexes are field-induced single molecule magnets, while their Ho analogs do not exhibit slow magnetic relaxation. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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12 pages, 3276 KiB  
Article
One-Dimensional Gadolinium (III) Complexes Based on Alpha- and Beta-Amino Acids Exhibiting Field-Induced Slow Relaxation of Magnetization
by Marta Orts-Arroyo, Adrián Sanchis-Perucho, Nicolas Moliner, Isabel Castro, Francesc Lloret and José Martínez-Lillo
Inorganics 2022, 10(3), 32; https://doi.org/10.3390/inorganics10030032 - 3 Mar 2022
Cited by 8 | Viewed by 2919
Abstract
Gadolinium (III) complexes exhibiting slow relaxation of magnetization are uncommon and have been much less studied than other compounds based on anisotropic lanthanide (III) ions. We prepared two one-dimensional gadolinium (III) complexes based on α-glycine (gly) and β-alanine (β-ala) amino acids, with the [...] Read more.
Gadolinium (III) complexes exhibiting slow relaxation of magnetization are uncommon and have been much less studied than other compounds based on anisotropic lanthanide (III) ions. We prepared two one-dimensional gadolinium (III) complexes based on α-glycine (gly) and β-alanine (β-ala) amino acids, with the formula {[Gd2(gly)6(H2O)4](ClO4)6·5H2O}n (1) and {[Gd2(β-ala)6(H2O)4](ClO4)6·H2O}n (2), which were magneto-structurally characterized. Compounds 1 and 2 crystallize in the triclinic system (space group Pī). In complex 1, two Gd (III) ions are eight-coordinate and bound to six oxygen atoms from six gly ligands and two oxygen atoms from two water molecules, the metal ions showing different geometries (bicapped trigonal prism and square antiprism). In complex 2, two Gd (III) ions are nine-coordinate and bound to seven oxygen atoms from six β-ala ligands and two oxygen atoms from two water molecules in the same geometry (capped square antiprism). Variable-temperature dc magnetic susceptibility measurements performed on microcrystalline samples of 1 and 2 show similar magnetic behavior for both compounds, with antiferromagnetic coupling between the Gd (III) ions connected through carboxylate groups. Ac magnetic susceptibility measurements reveal slow relaxation of magnetization in the presence of an external dc field in both compounds, hence indicating the occurrence of the field-induced single-molecule magnet (SMM) phenomenon in both 1 and 2. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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Graphical abstract

10 pages, 2566 KiB  
Article
Switching the Local Symmetry from D5h to D4h for Single-Molecule Magnets by Non-Coordinating Solvents
by Xia-Li Ding, Qian-Cheng Luo, Yuan-Qi Zhai, Qian Zhang, Lei Tian, Xinliang Zhang, Chao Ke, Xu-Feng Zhang, Yi Lv and Yan-Zhen Zheng
Inorganics 2021, 9(8), 64; https://doi.org/10.3390/inorganics9080064 - 16 Aug 2021
Cited by 2 | Viewed by 2846
Abstract
A solvent effect towards the performance of two single-molecule magnets (SMMs) was observed. The tetrahydrofuran and toluene solvents can switch the equatorial coordinated 4-Phenylpyridine (4-PhPy) molecules from five to four, respectively, in [Dy(OtBu)2(4-PhPy)5]BPh41 and Na{[Dy(O [...] Read more.
A solvent effect towards the performance of two single-molecule magnets (SMMs) was observed. The tetrahydrofuran and toluene solvents can switch the equatorial coordinated 4-Phenylpyridine (4-PhPy) molecules from five to four, respectively, in [Dy(OtBu)2(4-PhPy)5]BPh41 and Na{[Dy(OtBu)2(4-PhPy)4][BPh4]2}∙2thf∙hex 2. This alternation significantly changes the local coordination symmetry of the Dy(III) center from D5h to D4h for 1 and 2, seperately. Magnetic studies show that the magnetic anisotropy energy barrier of 2 is higher than that of 1, while the relation of blocking temperature is just on the contrary due to the symmetry effect. The calculations of the electrostatic potential successfully explained the driving force of solvents for the molecular structure change, confirming the feasibility of adjusting the performance of SMMs via diverse solvents. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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Graphical abstract

10 pages, 15647 KiB  
Article
A Dy(III) Fluorescent Single-Molecule Magnet Based on a Rhodamine 6G Ligand
by Lin Miao, Mei-Jiao Liu, Man-Man Ding, Yi-Quan Zhang and Hui-Zhong Kou
Inorganics 2021, 9(7), 51; https://doi.org/10.3390/inorganics9070051 - 29 Jun 2021
Cited by 3 | Viewed by 2443
Abstract
The complexes of lanthanide metals, especially dysprosium, can generally exhibit excellent magnetic properties. By means of modifying ligands, dual functions or even multi-functions can be achieved. Here, we synthesized an eight-coordinate Dy(III) complex 1, [Dy(HL-o)2(MeOH)2](ClO4)3 [...] Read more.
The complexes of lanthanide metals, especially dysprosium, can generally exhibit excellent magnetic properties. By means of modifying ligands, dual functions or even multi-functions can be achieved. Here, we synthesized an eight-coordinate Dy(III) complex 1, [Dy(HL-o)2(MeOH)2](ClO4)3·4.5MeOH, which is single-molecule magnet (SMM), and the introduction of the rhodamine 6G chromophore in the ring-opened ligand HL-o realizes ligand-centered fluorescence in addition to SMM. Magnetic measurements and ab initio calculations indicate that the magnetic relaxation for complex 1 should be due to the Raman relaxation process. Studies on magneto-structural correlationship of the rhodamine salicylaldehyde hydrazone Dy(III) complexes show that the calculated energy of the first Kramers Doublet (EKD1) is basically related to the Ophenoxy-Dy-Ophenoxy bond angle, i.e., the larger Ophenoxy-Dy-Ophenoxy bond angle corresponds to a larger EKD1. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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15 pages, 27420 KiB  
Article
Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand
by Bertrand Lefeuvre, Jessica Flores Gonzalez, Carlo Andrea Mattei, Vincent Dorcet, Olivier Cador and Fabrice Pointillart
Inorganics 2021, 9(7), 50; https://doi.org/10.3390/inorganics9070050 - 23 Jun 2021
Cited by 4 | Viewed by 2932
Abstract
The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam− = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6 [...] Read more.
The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam− = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6(L)]·2(C7H16) ((1)·2(C7H16)) and [Dy2((+)facam)6(L)]·2(C6H14) ((2)·2(C6H14)). The X-ray structures reveal that the L triad bridges two terminal Yb(hfac)3 or Dy(facam)3 units. (1)·2(C7H16) behaved as a near infrared YbIII centered emitter and a field-induced Single-Molecule Magnet (SMM) while (2)·2(C6H14) displayed SMM behavior in both zero- and in-dc field. The magnetization mainly relaxes through a Raman process for both complexes under an optimal applied magnetic field. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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