Multifunctional Molecule-based Magnetic Materials

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

Deadline for manuscript submissions: closed (31 July 2018) | Viewed by 13577

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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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Special Issue Information

Dear Colleagues,

Molecular magnetic materials fascinate both chemists and physicists since few decades for their potentials applications in a plethora of domains such as high-density data storage, sensors, spintronics and biology. Recent advances consist in combining within the same material several physical properties which can coexist or interact. One could highlight the famous synergy between chirality and molecular magnetism with the emergence of a third property i.e. magneto-chiral dichroism in enantiopure 3D-ordered ferromagnets and Single-Chain Magnets. Recently the coexistence of both luminescence and magnetism in molecular materials participate to increase the understanding level of the lanthanide magnetism by simple correlation between these properties. Optical activity, non-linear optical effects, electronic/proton conductivity, ferroelectricity, porosity…are other possible properties which could be combine in molecular magnetic materials to reach multi-properties systems and open the door to numerous amazing discoveries.

The purpose of this Special Issue is to cover latest advances in the elaboration and experimental/theoretical studies of multifunctional molecule-based magnetic materials through research article as well as review contributions.

Dr. Fabrice Pointillart
Guest Editor

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Keywords

  • Transition metal chemistry
  • Lanthanide and Actinide chemistry
  • Molecular Magnets
  • Photomagnetism
  • Electron transfer
  • Luminescence
  • Chirality
  • Ferroelectricity
  • Magneto-structural correlations

Published Papers (4 papers)

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Research

14 pages, 3615 KiB  
Article
Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative
by Gang Huang, Guillaume Calvez, Yan Suffren, Carole Daiguebonne, Stéphane Freslon, Olivier Guillou and Kevin Bernot
Magnetochemistry 2018, 4(4), 44; https://doi.org/10.3390/magnetochemistry4040044 - 3 Oct 2018
Cited by 9 | Viewed by 3350
Abstract
Up to now, even if murexide-based complexometric studies are performed with all 3d or 4f ions, the crystal structures of the light-lanthanide derivatives of the lanthanide-murexide series are unknown. In this work, we report the crystal structure of the NdIII derivative named [...] Read more.
Up to now, even if murexide-based complexometric studies are performed with all 3d or 4f ions, the crystal structures of the light-lanthanide derivatives of the lanthanide-murexide series are unknown. In this work, we report the crystal structure of the NdIII derivative named NdMurex. Contrary to all known complexes of the 3d or 4f series, a dimeric compound was obtained. As for its already reported DyIII and YbIII parents, the NdIII complex responsible for the color-change behaves as a single-molecule magnet (SMM). This behavior was observed on both the crystalline (NdMurex: Ueff = 6.20(0.80) K, 4.31 cm−1; τ0 = 2.20(0.92) × 10−5 s, Hdc = 1200 Oe) and anhydrous form (NdMurexAnhy: Ueff = 6.25(0.90) K, 4.34 cm−1; τ0 = 4.85(0.40) × 10−5 s, Hdc = 1200 Oe). The SMM behavior is reported also for the anhydrous CeIII derivative (CeMurexAnhy: Ueff = 5.40(0.75) K, 3.75 cm−1; τ0 = 3.02(1.10) × 10−5 s, Hdc = 400 Oe). The Near-Infrared Emission NIR emission was observed for NdMurexAnhy and highlights its bifunctionality. Full article
(This article belongs to the Special Issue Multifunctional Molecule-based Magnetic Materials)
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11 pages, 2435 KiB  
Article
How to Make a Better Magnet? Insertion of Additional Bridging Ligands into a Magnetic Coordination Polymer
by Gabriela Handzlik and Dawid Pinkowicz
Magnetochemistry 2018, 4(3), 41; https://doi.org/10.3390/magnetochemistry4030041 - 15 Sep 2018
Cited by 1 | Viewed by 3027
Abstract
A three-dimensional cyanide-bridged coordination polymer based on FeII (S = 2) and NbIV (S = 1/2) {[FeII(H2O)2]2[NbIV(CN)8]·4H2O}n (Fe2Nb) was modified [...] Read more.
A three-dimensional cyanide-bridged coordination polymer based on FeII (S = 2) and NbIV (S = 1/2) {[FeII(H2O)2]2[NbIV(CN)8]·4H2O}n (Fe2Nb) was modified at the self-assembly stage by inserting an additional formate HCOO bridge into its cyanide framework. The resulting mixed-bridged {(NH4)[(H2O)FeII-(μ-HCOO)-FeII(H2O)][NbIV(CN)8]·3H2O}n (Fe2NbHCOO) exhibited additional FeII-HCOO-FeII structural motifs connecting each of the two FeII centers. The insertion of HCOO was possible due to the substitution of some of the aqua ligands and crystallization water molecules in the parent framework by formate anions and ammonium cations. The formate molecular bridge not only shortened the distance between FeII ions in Fe2NbHCOO from 6.609 Å to 6.141 Å, but also created additional magnetic interaction pathways between the magnetic centers, resulting in an increase in the long range magnetic ordering temperature from 43 K for Fe2Nb to 58 K. The mixed-bridged Fe2NbHCOO also showed a much broader magnetic hysteresis loop of 0.102 T, compared to 0.013 T for Fe2Nb. Full article
(This article belongs to the Special Issue Multifunctional Molecule-based Magnetic Materials)
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11 pages, 3755 KiB  
Article
Slow Relaxation of the Magnetization in Bis-Decorated Chiral Helicene-Based Coordination Complexes of Lanthanides
by Jessica Flores Gonzalez, Vincent Montigaud, Nidal Saleh, Olivier Cador, Jeanne Crassous, Boris Le Guennic and Fabrice Pointillart
Magnetochemistry 2018, 4(3), 39; https://doi.org/10.3390/magnetochemistry4030039 - 5 Sep 2018
Cited by 12 | Viewed by 3512
Abstract
The complexes [Ln2(hfac)6(L)]·nC6H14 (Ln = Dy (1) n = 0, Yb (2) n = 1) with the L chiral 3,14-di-(2-pyridyl)-4,13-diaza[6]helicene ligand (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) have been synthesized in their [...] Read more.
The complexes [Ln2(hfac)6(L)]·nC6H14 (Ln = Dy (1) n = 0, Yb (2) n = 1) with the L chiral 3,14-di-(2-pyridyl)-4,13-diaza[6]helicene ligand (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) have been synthesized in their racemic form and structurally and magnetically characterized. Both complexes behave as field-induced single molecule magnets in the crystalline phase. These magnetic properties were rationalized by ab initio calculations. Full article
(This article belongs to the Special Issue Multifunctional Molecule-based Magnetic Materials)
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20 pages, 1711 KiB  
Article
Heterobimetallic One-Dimensional Coordination Polymers MICuII (M = Li and K) Based on Ferromagnetically Coupled Di- and Tetracopper(II) Metallacyclophanes
by Tamyris T. da Cunha, Willian X. C. Oliveira, Emerson F. Pedroso, Francesc Lloret, Miguel Julve and Cynthia L. M. Pereira
Magnetochemistry 2018, 4(3), 38; https://doi.org/10.3390/magnetochemistry4030038 - 25 Aug 2018
Cited by 5 | Viewed by 3112
Abstract
The synthesis, crystal structure and magnetic properties of the coordination polymers of formula [EDAP{Li6(H2O)8[(Cu2(μ-mpba)2)2(H2O)2]}]n (1) and [(EDAP)2{K(H2O)4[Cu2 [...] Read more.
The synthesis, crystal structure and magnetic properties of the coordination polymers of formula [EDAP{Li6(H2O)8[(Cu2(μ-mpba)2)2(H2O)2]}]n (1) and [(EDAP)2{K(H2O)4[Cu2(μ-mpba)2(H2O)2]}Cl·2H2O]n (2), in which mpba = N,N′-1,3-phenylenebis(oxamate) and EDAP2+ = 1,1′-ethylenebis(4-aminopyridinium) are described. Both compounds have in common the presence of the [Cu2(mpba)2]4− tetraanionic unit which is a [3,3] metallacyclophane motif in which the copper(II) ions are five-coordinate in a distorted square pyramidal surrounding. The complex anion in 1 is dimerized through double out-of-plane copper to outer carboxylate-oxygen atoms resulting in the centrosymmetric tetracopper(II) fragment [Cu4(μ-mpba)4(H2O)2]8− which act as a ligand toward six hydrated lithium(I) cations leading to anionic ladder-like double chains whose charge is neutralized by the EDAP2+ cations. In the case of 2, each dicopper(II) entity acts as a ligand towards tetraquapotassium(I) units to afford anionic zig zag single chains of formula {K(H2O)4[Cu2(μ-mpba)2(H2O)2]}n3n− plus EDAP2+ cations and non-coordinate chloride anions. Cryomagnetic measurements on polycrystalline samples 1 and 2 show the occurrence of ferromagnetic interactions between the copper(II) ions across the –Namidate–(C–C–C)phenyl–Namidate– exchange pathway [J = +10.6 (1) and +8.22 cm−1 (2)] and antiferromagnetic ones through the double out-of-plane carboxylate-oxygen atoms [j = −0.68 cm−1 (1), the spin Hamiltonian being defined as H = J ( S C u 1 · S C u 2 + S C u 2 i · S C u 1 i ) j ( S C u 2 · S C u 2 i ) ]. Full article
(This article belongs to the Special Issue Multifunctional Molecule-based Magnetic Materials)
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