Redox-Active Dysprosium Single-Molecule Magnet: Spectro-Electrochemistry and Theoretical Investigations

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Field-Induced Dysprosium Single-Molecule Magnet Based on a Redox-Active Fused 1,10-Phenanthroline-Tetrathiafulvalene-1,10-Phenanthroline Bridging Triad

Tetrathiafulvalene and 1,10-phenanthroline moieties present, respectively remarkable redox-active and complexation activities. In this work, we investigated the coordination reaction between the bis(1,10-phenanthro[5,6-b])tetrathiafulvalene triad (L) and the Dy(hfac)3·2H2O metallo precursor. The resulting {[Dy2(hfac)6(L)]·CH2Cl2·C6H14}3 (1) dinuclear complex showed a crystal structure in which the triad L bridged two terminal Dy(hfac)3 units and the supramolecular co-planar arrangement of the triads is driven by donor-acceptor interactions. The frequency dependence of the out-of-phase component of the magnetic susceptibility highlights three distinct maxima under a 2000 Oe static applied magnetic field, a sign that 1 displays a Single-Molecule Magnet (SMM) behavior with multiple magnetic relaxations. Ab initio calculations rationalized the Ising character of the magnetic anisotropy of the DyIII ions and showed that the main anisotropy axes are perpendicular to the co-planar arrangement of the triads. Single-crystal rotating magnetometry confirms the orientation of the main magnetic axis. Finally combining structural analysis and probability of magnetic relaxation pathways through Quantum Tunneling of the Magnetization (QTM) vs. excited states (Orbach), each DyIII center has been attributed to one of the three observed magnetic relaxation times. Such coordination compound can be considered as an ideal candidate to perform redox-magnetic switching

Reuse of medical face masks in domestic and community settings without sacrificing safety: Ecological and economical lessons from the Covid-19 pandemic

The need for personal protective equipment increased exponentially in response to the Covid-19 pandemic. To cope with the mask shortage during springtime 2020, a French consortium was created to find ways to reuse medical and respiratory masks in healthcare departments. The consortium addressed the complex context of the balance between cleaning medical masks in a way that maintains their safety and functionality for reuse, with the environmental advantage to manage medical disposable waste despite the current mask designation as single-use by the regulatory frameworks. We report a Workflow that provides a quantitative basis to determine the safety and efficacy of a medical mask that is decontaminated for reuse. The type IIR polypropylene medical masks can be washed up to 10 times, washed 5 times and autoclaved 5 times, or washed then sterilized with radiations or ethylene oxide, without any degradation of their filtration or breathability properties. There is loss of the antiprojection properties. The Workflow rendered the medical masks to comply to the AFNOR S76-001 standard as “type 1 non-sanitory usage masks”. This qualification gives a legal status to the Workflow-treated masks and allows recommendation for the reuse of washed medical masks by the general population, with the significant public health advantage of providing better protection than cloth-tissue masks. Additionally, such a legal status provides a basis to perform a clinical trial to test the masks in real conditions, with full compliance with EN 14683 norm, for collective reuse. The rational reuse of medical mask and their end-of-life management is critical, particularly in pandemic periods when decisive turns can be taken. The reuse of masks in the general population, in industries, or in hospitals (but not for surgery) has significant advantages for the management of waste without degrading the safety of individuals wearing reused masks

Dysprosium Single-Molecule Magnets Involving 1,10-Phenantroline-5,6-dione Ligand

International audienceThe two mononuclear complexes of the formula [Dy(tta)(3)(L)] (1) and [Dy(hfac)(3)(L)] (2) (where tta(-) = 2-thenoytrifluoroacetylacetonate and hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate) were obtained from the coordination reaction of the Dy(tta)(3)center dot 2H(2)O or Dy(hfac)(3)center dot 2H(2)O units with the 1,10-phenantroline-5,6-dione ligand (L). Their structures have been determined by X-ray diffraction studies on single crystals, and they revealed a supramolecular assembly of tetramers through sigma-pi interactions. Both complexes displayed a Single-Molecule Magnet (SMM) behavior without an external applied magnetic field. Magnetic relaxation happened through Orbach, Raman and Quantum Tunneling of the Magnetization (QTM). Wavefunction theory calculations were realized to rationalize the magnetic properties

Dysprosium(III) compounds assembled via a versatile ligand incorporating salicylic hydrazide and 8-hydroxyquinolin units: syntheses, structures and magnetic properties

International audienceAssembly of dysprosium(iii) salts with a multidentate ligand H3L ((2-hydroxy)-N'-((8-hydroxyquinolin-2-yl)methylene)-benzohydrazide) affords a variety of products with different topological structures, namely [Dy(H2L)(HL)]·CH3OH (1), [Dy2(HL)2(C6H5COO)2(CH3OH)2]·3CH3OH (2), [Dy2(HL)2(NO3)2(DMF)4]·4DMF (3), [Dy4L4(CH3OH)4]·2CH3OH·4H2O (4) and ([Dy4(HL)4(C6H5COO)4(CH3OH)(H2O)]·2CH3OH·CH3CN·H2O)n (5). The versatile and flexible coordination modes of phenoxo groups from salicylic hydrazide prove to be a key factor in the assembly of corresponding structures depending upon the reaction conditions. It is noteworthy that ligands HL2- act as a long-distance link and further connect the Dy2 fragments into an infinite 1D chain due to the conformational flexibility resulting from the rotatable C-C bond in 5. Furthermore, the magnetic measurements were performed on all complexes. The dc magnetic susceptibility data evidence distinct magnetic coupling interactions in the dinuclear complexes 2 (antiferromagnetic) and 3 (ferromagnetic) despite their similar structures, and only complex 3 shows slow relaxation behavior of magnetization. Ab initio calculations and electrostatic potential analysis on complexes 2, 3, and three other complexes (6, 7, 8) incorporating different kinds of ligands reveal the important interrelationship of magnetic anisotropy, magnetic coupling interactions and SMM properties

Solvato Modulation of the Magnetic Memory in Isotopically Enriched Erbium Polyoxometallate

International audienceSingle-Molecule Magnet (SMM) property is by essence molecular, while commonly measured in solid crystalline state. Solvent crystallization molecules are usually neglected in the analysis and interpretation of solid-state properties. The solvation/desolvation process in the polyoxometalate(POM)-based Na [Er(W O ) ] ⋅ 35 H O SMM demonstrates that the dehydrated form relaxes more than 1000 times faster than the initial state, while the rehydration process allows the quasi complete recovering of the initial magnetic behaviour. This dehydration process is monitored by thermogravimetric analysis (TGA) and temperature-dependent X-ray powder diffraction, and rationalized by periodic quantum chemical calculations evidencing the tremendous role of the labile water molecules in the stability of the edifice. Ab-initio calculations highlight that sodium ions localization in the structure drive the magnetic responses. Isotopic enrichment with nuclear spin free ( Er, I=0) Er ions shows that the relaxation dynamics in the quantum regime depends on the nuclear spin

Tetranuclear dysprosium single-molecule magnets tunable magnetic interactions and magnetization dynamics through modifying coordination number

International audienceThe study of mononuclear lanthanide-based systems, where the observed Single Molecule Magnets (SMMs) properties originate from the local magnetic anisotropy of the single lanthanide ion, has been extensively investigated in the literature. The case for polynuclear lanthanide SMMs becomes more challenging both experimentally and theoretically due to the complexity of such architectures involving interactions between the magnetic centers. Much interest was devoted to the study of the structural effect on the magnetic interactions and relaxation dynamics. However, the understanding of the structural influence on those two factors remains a difficult task. To address this issue, a system containing two structurally related tetranuclear Dy(iii) SMMs, namely [Dy4(L)4(OH)2(DMF)4(NO3)2]·2(DMF)·(H2O) (1) and [Dy4(L)4(OH)2(DMF)2(NO3)2] (2) (H2L = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol), is introduced and investigated. Through modifying the ligands on the changeable coordination sites, the intramolecular magnetic interactions and relaxation dynamics in these two Dy(iii)4 SMMs can be tuned. Both complexes exhibit slow relaxation of their magnetization with a relaxation barrier of 114 K for complex 2 while a blocking temperature below 2 K is observed for complex 1. Ab initio calculations reveal that changes in coordination numbers and geometries on the Dy(iii) sites can significantly affect the magnetic interactions as well as single-ion anisotropy. The combination of experimental work and ab initio calculations offers insight into the relationship between structures and magnetic properties and sheds light on the rational design of future polynuclear lanthanide SMMs with enhanced magnetic properties

Slow Relaxation of the Magnetization in Bis-Decorated Chiral Helicene-Based Coordination Complexes of Lanthanides

International audienceThe complexes [Ln(2)(hfac)(6)(L)](.)nC(6)H(14) (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

Tuning the Magnetic Interactions in Dy(III)4 Single-Molecule Magnets

International audienceThe study of mononuclear lanthanide-based systems, where the observed single-molecule magnets (SMMs) properties originate from the local description of the magnetic properties of the lanthanide ion, has been widely investigated through the literature. The case of polynuclear SMMs becomes more challenging both experimentally and theoretically due to the complexity of such architectures involving interactions between the magnetic centers. Many efforts have been focused on the understanding of the nature of these interactions and their effects on the SMM properties. In this work, a series of three structurally related tetranuclear dysprosium(III) SMMs, namely, [Dy(L)(OH)(DMF)(NO)]·2(DMF)·(HO) (1), [Dy(L)(OH)(DMF)(tfaa)]·2(CHCN) (2), and [Dy(L)(OH)(DMF)(acac)]·2(DMF) (3) (HL = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol, Htfaa = trifluoroacetylactone, Hacac = acetylacetonate), has been synthesized and investigated. By a fine-tuning of the ligands on the changeable coordination sites in these Dy(III) SMMs, the intramolecular magnetic interactions can be modified, switching from antiferromagnetic (for 1 and 2) to ferromagnetic (for 3). Ab initio calculations support these statements. In addition, the formation of 1 has been analyzed by ESI-MS analysis of the reaction mixture, indicating rather quick and high-yield formation of the [Dy] framework in solution. The combination of experimental work and ab initio calculations offers further insight into the relationship between structures and magnetic properties and sheds light on how to tune magnetic interactions in future polynuclear dysprosium complexes

Reversible Pressure-Magnetic Modulation in a Tetrathiafulva-lene-Based Dyad Piezochromic Dysprosium Single-Molecule Magnet

The extreme sensitivity of trivalent lanthanide ions to crystal field variations led to the emergence of single-molecule mag-netic switching under various stimuli. The use of pressure as an external stimulus instead of classic light irradiation, oxidation or any chemical reactions allows a fine tuning of the magnetic modulation. Here the well-known pure isotopically enriched [162Dy(tta)3(L)]C6H14 (162Dy) Single-Molecule Magnet (SMM) (tta- = 2-2-thenoyltrifluoroacetonate and L = 4,5-bis(propylthio)-tetrathiafulvalene-2-(2-pyridyl)benzimidazole-methyl-2-pyridine) was experimentally investigated by single-crystal diffraction and squid magnetometry under high applied pressures. Both reversible piezochromic properties and pres-sure modulation of the SMM behavior were demonstrated and supported by ab initio calculations. The magnetic study of the diluted sample [162Dy0.05Y0.95(tta)3(L)]C6H14 (162Dy@Y) indicated that variations in the electronic structure have both intra- and inter-molecular origins. Quantitative magnetic interpretation concludes to a deterioration of the Orbach process for the benefit of both Raman and QTM mechanisms under applied pressure