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Magnetochemistry
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Transition Metal (3d,4d,5d) and Lanthanide(III) Based Complexes and Coordination Polymers...
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Transition Metal (3d,4d,5d) and Lanthanide(III) Based Complexes and Coordination Polymers Showing Single-Molecule Magnet Behaviour

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

Deadline for manuscript submissions: closed (1 July 2021) | Viewed by 10950

Special Issue Editor

Dr. Javier Cepeda

E-Mail Website
Guest Editor
Department of Applied Chemistry, Chemistry Faculty, University of the Basque Country (UPV/EHU), Paseo Manuel de Lardizabal, no. 3, Donostia-San Sebastián, Spain
Interests: metal-organic frameworks (MOFs); photoluminescent properties of MOFs; adsorption of pollutant and combustible gases on MOFs; MOF-based long-lasting phosphors; MOF-based sensors
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Single-molecule magnets (SMMs) are in theory the smallest possible components for spin-based electronic devices, among which data storage is one of the most laureate applications. The feasibility of SIMs depends mainly on the correct molecular design focused on two major factors in such a way that the resulting metal–organic systems exhibit: (i) large energy barriers that prevent reversal of the magnetization (Ueff) as well as the highest possible blocking temperature (TB) and (ii) ordered structures that distribute spin carriers into addressable arrays. Taking into account that the energy barrier (Ueff) is governed by the magnetic anisotropy of the complex and the spin ground state, transition metals (TM) have proven to be good candidates to give rise to SIMs since, coordinated to adequate ligands, their d orbitals are propitiously split by the field, while they are spatially arranged into isolated molecules or 1-, 2-, and 3-dimensional materials which present interesting structural and physical properties. Moreover, the large spin states available for lanthanide(III) ions, some of which are known to exhibit high magnetic anisotropy, occupy an honored position to build SMMs. This Special Issue of the open access journal Magnetochemistry, devoted to SIMs, provides an excellent opportunity to researchers working in the field to publish their most recent discoveries.

Dr. Javier Cepeda
Guest Editor

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Keywords

  • Transition metal ions
  • Lanthanide(III) metal ions
  • Slow relaxation of the magnetization
  • SMMs based on isolated molecules
  • SMMs consisting of coordination polymers

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Published Papers (3 papers)

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18 pages, 2495 KiB  
Article
Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3d-4f Complexes
by Itziar Oyarzabal, Estitxu Echenique-Errandonea, Eider San Sebastián, Antonio Rodríguez-Diéguez, José Manuel Seco and Enrique Colacio
Magnetochemistry 2021, 7(2), 22; https://doi.org/10.3390/magnetochemistry7020022 - 5 Feb 2021
Cited by 9 | Viewed by 2808
Abstract
New dinuclear MII-LnIII complexes of general formulas [Cu(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN·H2O (LnIII = Gd (1), Tb (2), Dy (3) and Er (4)), [Ni(CH3CN)(µ-L)(µ-OAc)Ln(NO3 [...] Read more.
New dinuclear MII-LnIII complexes of general formulas [Cu(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN·H2O (LnIII = Gd (1), Tb (2), Dy (3) and Er (4)), [Ni(CH3CN)(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (LnIII = Nd (5), Gd (6), Tb (7), Dy (8), Er (9) and Y (10)) and [Co(CH3CN)(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (LnIII = Gd (11), Tb (12), Dy (13), Er (14) and Y (15)) were prepared from the compartmental ligand N,N′-dimethyl-N,N′-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the transition metal ions occupy the internal N2O2 coordination site of the ligand, whereas the LnIII ions lie in the O4 external site. Both metallic ions are connected by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged MIILnIII compounds. Direct current (dc) magnetic measurements allow the study of the magnetic exchange interactions between the 3d and 4f metal ions, which is supported by density functional theory (DFT) theoretical calculations for the GdIII-based counterparts. Due to the weak ferromagnetic exchange coupling constants obtained both experimentally and theoretically, the magneto-thermal properties of the less anisotropic systems (compounds 1 and 6) are also studied. Alternating current (ac)magnetic measurements reveal the occurrence of slight frequency dependency of the out-of-phase signal for complexes 8, 9 and 13, while complex 15 displays well-defined maximums below ~6 K. Full article
(This article belongs to the Special Issue Transition Metal (3d,4d,5d) and Lanthanide(III) Based Complexes and Coordination Polymers Showing Single-Molecule Magnet Behaviour)
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20 pages, 4638 KiB  
Article
Single-Ion Magnet and Photoluminescence Properties of Lanthanide(III) Coordination Polymers Based on Pyrimidine-4,6-Dicarboxylate
by Oier Pajuelo-Corral, Jose Angel García, Oscar Castillo, Antonio Luque, Antonio Rodríguez-Diéguez and Javier Cepeda
Magnetochemistry 2021, 7(1), 8; https://doi.org/10.3390/magnetochemistry7010008 - 4 Jan 2021
Cited by 11 | Viewed by 4155
Abstract
Herein, we report the magnetic and photoluminescence characterization of coordination polymers (CP) built from the combination of lanthanide(III) ions, pyrimidine-4,6-dicarboxylate (pmdc) ligand and a co-ligand with formula {[Dy(μ-pmdc)(μ-ox)0.5(H2O)3]·2H2O}n (1-Dy), {[Dy(μ3-pmdc)(μ-ox) [...] Read more.
Herein, we report the magnetic and photoluminescence characterization of coordination polymers (CP) built from the combination of lanthanide(III) ions, pyrimidine-4,6-dicarboxylate (pmdc) ligand and a co-ligand with formula {[Dy(μ-pmdc)(μ-ox)0.5(H2O)3]·2H2O}n (1-Dy), {[Dy(μ3-pmdc)(μ-ox)0.5(H2O)2] ~2.33H2O}n (2-Dy), {[Dy2(μ3-pmdc)(μ4-pmdc)(μ-ox)(H2O)3]·5H2O}n (3-Dy), {[Ln(μ3-pmdc)(μ-ox)0.5(H2O)2]·H2O}n (where Ln(III) = Nd (4-Nd), Sm (4-Sm), Eu (4-Eu) and Dy (4-Dy)) and {[Dy(μ4-pmdc)(NO3)(H2O)]·H2O}n (5-Dy). It must be noted the presence of oxalate anion acting as ditopic co-ligand in compounds 1-Dy, 2-Dy, 3-Dy and 4-Ln, whereas in 5-Dy the nitrate anion plays the role of terminal co-ligand. Direct current measurements carried out for the dysprosium-based CPs reveal almost negligible interactions between Dy3+ ions within the crystal structure, which is confirmed by computed values of the exchange parameters J. In addition, alternating current measurements show field-induced single-molecule magnet (SMM) behavior in compounds 1-Dy, 2-Dy, 4-Dy and 5-Dy, whereas slight-frequency dependence is also observed in 3-Dy. Solid state emission spectra performed at room temperature for those compounds emitting in visible region confirm the occurrence of significant ligand-to-lanthanide charge transfer in view of the strong characteristic emissions for all lanthanide ions. Emission decay curves were also recorded to estimate the emission lifetimes for the reported compounds, in addition to the absolute quantum yields. Among them, the high quantum yield of 25.0% measured for 4-Eu is to be highlighted as a representative example of the good emissive properties of the materials. Full article
(This article belongs to the Special Issue Transition Metal (3d,4d,5d) and Lanthanide(III) Based Complexes and Coordination Polymers Showing Single-Molecule Magnet Behaviour)
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11 pages, 1894 KiB  
Article
Slow Magnetic Relaxation in a One-Dimensional Coordination Polymer Constructed from Hepta-Coordinate Cobalt(II) Nodes
by Amit Kumar Mondal, Arpan Mondal and Sanjit Konar
Magnetochemistry 2020, 6(4), 45; https://doi.org/10.3390/magnetochemistry6040045 - 23 Sep 2020
Cited by 12 | Viewed by 3163
Abstract
A one-dimensional coordination polymer was synthesized employing hepta-coordinate CoII as nodes and dicyanamide as linkers. Detailed direct current (DC) and alternating current (AC) magnetic susceptibility measurements reveal the presence of field-induced slow magnetic relaxation behavior of the magnetically isolated seven-coordinate CoII [...] Read more.
A one-dimensional coordination polymer was synthesized employing hepta-coordinate CoII as nodes and dicyanamide as linkers. Detailed direct current (DC) and alternating current (AC) magnetic susceptibility measurements reveal the presence of field-induced slow magnetic relaxation behavior of the magnetically isolated seven-coordinate CoII center with an easy-plane magnetic anisotropy. Detailed ab initio calculations were performed to understand the magnetic relaxation processes. To our knowledge, the reported complex represents the first example of slow magnetic relaxation in a one-dimensional coordination polymer constructed from hepta-coordinate CoII nodes and dicyanamide linkers. Full article
(This article belongs to the Special Issue Transition Metal (3d,4d,5d) and Lanthanide(III) Based Complexes and Coordination Polymers Showing Single-Molecule Magnet Behaviour)
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