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- ItemSingle-Electron Lanthanide-Lanthanide Bonds Inside Fullerenes toward Robust Redox-Active Molecular Magnets(Washington, DC : ACS Publications, 2019) Liu, Fupin; Spree, Lukas; Krylov, Denis S.; Velkos, Georgios; Avdoshenko, Stanislav M.; Popov, Alexey A.A characteristic phenomenon of lanthanide-fullerene interactions is the transfer of metal valence electrons to the carbon cage. With early lanthanides such as La, a complete transfer of six valence electrons takes place for the metal dimers encapsulated in the fullerene cage. However, the low energy of the σ-type Ln-Ln bonding orbital in the second half of the lanthanide row limits the Ln2 → fullerene transfer to only five electrons. One electron remains in the Ln-Ln bonding orbital, whereas the fullerene cage with a formal charge of -5 is left electron-deficient. Such Ln2@C80 molecules are unstable in the neutral form but can be stabilized by substitution of one carbon atom by nitrogen to give azafullerenes Ln2@C79N or by quenching the unpaired electron on the fullerene cage by reacting it with a chemical such as benzyl bromide, transforming one sp2 carbon into an sp3 carbon and yielding the monoadduct Ln2@C80(CH2Ph). Because of the presence of the Ln-Ln bonding molecular orbital with one electron, the Ln2@C79N and Ln2@C80(R) molecules feature a unique single-electron Ln-Ln bond and an unconventional +2.5 oxidation state of the lanthanides.In this Account, which brings together metallofullerenes, molecular magnets, and lanthanides in unconventional valence states, we review the progress in the studies of dimetallofullerenes with single-electron Ln-Ln bonds and highlight the consequences of the unpaired electron residing in the Ln-Ln bonding orbital for the magnetic interactions between Ln ions. Usually, Ln···Ln exchange coupling in polynuclear lanthanide compounds is weak because of the core nature of 4f electrons. However, when interactions between Ln centers are mediated by a radical bridge, stronger coupling may be achieved because of the diffuse nature of radical-based orbitals. Ultimately, when the role of a radical bridge is played by a single unpaired electron in the Ln-Ln bonding orbital, the strength of the exchange coupling is increased dramatically. Giant exchange coupling in endohedral Ln2 dimers is combined with a rather strong axial ligand field exerted on the lanthanide ions by the fullerene cage and the excess electron density localized between two Ln ions. As a result, Ln2@C79N and Ln2@C80(CH2Ph) compounds exhibit slow relaxation of magnetization and exceptionally high blocking temperatures for Ln = Dy and Tb. At low temperatures, the [Ln3+-e-Ln3+] fragment behaves as a single giant spin. Furthermore, the Ln-Ln bonding orbital in dimetallofullerenes is redox-active, which allows its population to be changed by electrochemical reactions, thus changing the magnetic properties because the change in the number of electrons residing in the Ln-Ln orbital affects the magnetic structure of the molecule. © 2019 American Chemical Society.
- ItemStructure evolution of soft magnetic (Fe36Co36B19.2Si4.8Nb4)100-xCux (x = 0 and 0.5) bulk glassy alloys(Amsterdam [u.a.] : Elsevier Science, 2015) Stoica, Mihai; Ramasamy, Parthiban; Kaban, Ivan; Scudino, Sergio; Nicoara, Mircea; Vaughan, Gavin B.M.; Wright, Jonathan; Kumar, Ravi; Eckert, JürgenFully amorphous rods with diameters up to 2 mm diameter were obtained upon 0.5 at.% Cu addition to the Fe36Co36B19.2Si4.8Nb4 bulk metallic glass. The Cu-added glass shows a very good thermal stability but, in comparison with the Cu-free base alloy, the entire crystallization behavior is drastically changed. Upon heating, the glassy (Fe36Co36B19.2Si4.8Nb4)99.5Cu0.5 samples show two glass transitions-like events, separated by an interval of more than 100 K, in between which a bcc-(Fe,Co) solid solution is formed. The soft magnetic properties are preserved upon Cu-addition and the samples show a saturation magnetization of 1.1 T combined with less than 2 A/m coercivity. The relaxation behavior prior to crystallization, as well as the crystallization behavior, were studied by time-resolved X-ray diffraction using synchrotron radiation. It was found that both glassy alloys behave similar at temperatures below the glass transition. Irreversible structural transformations take place when approaching the glass transition and in the supercooled liquid region.
- ItemSyntheses, crystal structure and magnetic properties of Tl9RETe6 (RE = Ce, Sm, Gd)(Basel : MDPI AG, 2020) Isaeva, A.; Schönemann, R.; Doert, T.The three compounds Tl9RETe6 with RE = Ce, Sm, Gd were synthesized from the elements at 1020 K. Their isostructural crystal structures are ordered derivatives of the Tl5Te3 type with rare-earth metal and thallium occupying different Wyckoff positions. The structures can be understood as charge-ordered in accordance with the Zintl-Klemm concept: 9 Tl+ + RE3+ + 6 Te2-. DFT calculations for Tl9GdTe6, however, result in a low, but finite density of states at the Fermi level. Magnetic data confirm trivalent Gd, but indicate a small amount of Ce4+ in Tl9CeTe6; no indications for long-range magnetic order was found down to T = 2 K.
- ItemRecent advances in single molecule magnetism of dysprosium-metallofullerenes(Cambridge : Royal Society of Chemistry, 2019) Spree, L.; Popov, A.A.This article outlines the magnetic properties of single molecule magnets based on Dy-encapsulating endohedral metallofullerenes. The factors that govern these properties, such as the influence of different non-metal species in clusterfullerenes, the cage size, and cage isomerism are discussed, as well as the recent successful isolation of dimetallofullerenes with unprecedented magnetic properties. Finally, recent advances towards the organization of endohedral metallofullerenes in 1D, 2D, and 3D ordered structures with potential for devices are reviewed.
- ItemPhase transition and anomalous low temperature ferromagnetic phase in Pr 0.6Sr 0.4MnO 3 single crystals(New York, NY : Springer Science + Business Media B.V., 2009) Rößler, S.; Harikrishnan, S.; Naveen Kumar, C.M.; Bhat, H.L.; Elizabeth, S.; Rößler, U.K.; Steglich, F.; Wirth, S.We report on the magnetic and electrical properties of Pr 0.6Sr 0.4MnO 3 single crystals. This compound undergoes a continuous paramagnetic-ferromagnetic transition with a Curie temperature T C301 K and a first-order structural transition at T S64 K. At T S, the magnetic susceptibility exhibits an abrupt jump, and a corresponding small hump is seen in the resistivity. The critical behavior of the static magnetization and the temperature dependence of the resistivity are consistent with the behavior expected for a nearly isotropic ferromagnet with short-range exchange belonging to the Heisenberg universality class. The magnetization (M-H) curves below T S are anomalous in that the virgin curve lies outside the subsequent M-H loops. The hysteretic structural transition at T S as well as the irreversible magnetization processes below T S can be explained by phase separation between a high-temperature orthorhombic and a low-temperature monoclinic ferromagnetic phase.
- ItemImpact of Mn-Pn intermixing on magnetic properties of an intrinsic magnetic topological insulator: the µSR perspective(Bristol : IOP Publ., 2023) Sahoo, M.; Salman, Z.; Allodi, G.; Isaeva, A.; Folkers, L.; Wolter, A.U.B.; Büchner, B.; De Renzi, R.We investigated the magnetic properties of polycrystalline samples of the intrinsic magnetic topological insulators MnPn2Te4, with pnictogen Pn = Sb, Bi, by bulk magnetization and μSR. DC susceptibility detects the onset of magnetic ordering at TN = 27 K and 24 K and a field dependence of the macroscopic magnetization compatible with ferri- (or ferro-) and atiferro- magnetic ordering, respectively. Weak transverse field (wTF) Muon Spin Rotation (μSR) confirms the homogeneous bulk nature of magnetic ordering at the same two distinct transition temperatures. Zero Field (ZF) μSR shows that the Sb based material displays a broader distribution of internal field at the muon, in accordance with a larger deviation from the stoichiomectric composition and a higher degree of positional disorder (Mn at the Pn(6c) site), which however does not affect significantly the sharpness of the thermodynamic transition, as detected by the muon magnetic volume fraction and the observability of a critical divergence in the longitudinal and transverse muon relaxation rates.
- ItemDiscovery, Crystal Growth, and Characterization of Garnet Eu2PbSb2Zn3O12(Weinheim : Wiley-VCH, 2020) Morrow, Ryan; Sturza, Mihai I.; Ray, Rajyavardhan; Himcinschi, Cameliu; Kern, Jonas; Schlender, Philipp; Richter, Manuel; Wurmehl, Sabine; Büchner, BerndSingle crystal specimens of previously unknown garnet Eu2PbSb2Zn3O12 were grown in a reactive PbO:PbF2 flux medium. The crystals were characterized by a combination of X-ray crystallography, magnetization measurements, and the optical techniques of Raman, photoluminescence, and UV/Vis spectroscopy. The material exhibits Van Vleck paramagnetism associated with the J = 0 state of Eu3+, which was possible to accurately fit to a theoretical model. Band structure calculations were performed and compared to the experimental band gap of 1.98 eV. The crystals demonstrate photoluminescence associated with the 4f 6 configuration of the Eu3+ ions sitting at the distorted 8-coordinate garnet A site. The title compound represents a unique quinary contribution to a relatively unexplored area of rare earth bearing garnet crystal chemistry. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemReversible magnetism switching of iron oxide nanoparticle dispersions by controlled agglomeration(Cambridge : Royal Society of Chemistry, 2021) Müssig, Stephan; Kuttich, Björn; Fidler, Florian; Haddad, Daniel; Wintzheimer, Susanne; Kraus, Tobias; Mandel, KarlThe controlled agglomeration of superparamagnetic iron oxide nanoparticles (SPIONs) was used to rapidly switch their magnetic properties. Small-angle X-ray scattering (SAXS) and dynamic light scattering showed that tailored iron oxide nanoparticles with phase-changing organic ligand shells agglomerate at temperatures between 5 °C and 20 °C. We observed the concurrent change in magnetic properties using magnetic particle spectroscopy (MPS) with a temporal resolution on the order of seconds and found reversible switching of magnetic properties of SPIONs by changing their agglomeration state. The non-linear correlation between magnetization amplitude from MPS and agglomeration degree from SAXS data indicated that the agglomerates' size distribution affected magnetic properties.
- ItemTailoring biocompatible Ti-Zr-Nb-Hf-Si metallic glasses based on high-entropy alloys design approach(Amsterdam : Elsevier, 2020) Calin, Mariana; Vishnu, Jithin; Thirathipviwat, Pramote; Popa, Monica-Mihaela; Krautz, Maria; Manivasagam, Geetha; Gebert, AnnettPresent work unveils novel magnetic resonance imaging (MRI) compatible glassy Ti-Zr-Nb-Hf-Si alloys designed based on a high entropy alloys approach, by exploring the central region of multi-component alloy phase space. Phase analysis has revealed the amorphous structure of developed alloys, with a higher thermal stability than the conventional metallic glasses. The alloys exhibit excellent corrosion properties in simulated body fluid. Most importantly, the weak paramagnetic nature (ultralow magnetic susceptibility) and superior radiopacity (high X-ray attenuation coefficients) offer compatibility with medical diagnostic imaging systems thereby opening unexplored realms for biomedical applications.
- ItemSingle-crystalline FeCo nanoparticle-filled carbon nanotubes: Synthesis, structural characterization and magnetic properties(Frankfurt am Main : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2018) Ghunaim, R.; Scholz, M.; Damm, C.; Rellinghaus, B.; Klingeler, R.; Büchner, B.; Mertig, M.; Hampel, S.In the present work, we demonstrate different synthesis procedures for filling carbon nanotubes (CNTs) with equimolar binary nanoparticles of the type Fe-Co. The CNTs act as templates for the encapsulation of magnetic nanoparticles and provide a protective shield against oxidation as well as prevent nanoparticle agglomeration. By variation of the reaction parameters, we were able to tailor the sample purity, degree of filling, the composition and size of the filling particles, and therefore, the magnetic properties. The samples were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), superconducting quantum interference device (SQUID) and thermogravimetric analysis (TGA). The Fe-Co-filled CNTs show significant enhancement in the coercive field as compared to the corresponding bulk material, which make them excellent candidates for several applications such as magnetic storage devices.