Magnetic Relaxation Processes Research Articles

Synthesis of nanogranular Fe3O4/biomimetic hydroxyapatite for potential applications in nanomedicine: structural and magnetic characterization

We realized the synthesis of a novel nanogranular system consisting of magnetite nanoparticles embedded in biomimetic carbonate hydroxyapatite (HA), for prospective uses in bone tissue engineering. An original two-step method was implemented: in the first step, magnetite nanoparticles are prepared by refluxing an aqueous solution of Fe(SO4) and Fe2(SO4)3 in an excess of tetrabutilammonium hydroxide acting as surfactant; then, the magnetite nanoparticles are coated with a Ca(OH)2 layer, to induce the growth of HA directly on their surface, by reaction of Ca(OH)2 with HPO42−. Two nanogranular samples were collected with magnetite content ∼0.8 and ∼4 wt%. The magnetite nanoparticles and the composite material were investigated by x-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. These analyses provided information on the structure of the nanoparticles (mean size ∼6 nm) and revealed the presence of surface hydroxyl groups, which promoted the subsequent growth of the HA phase, featuring a nanocrystalline lamellar structure. The magnetic study, by a superconducting quantum interference device magnetometer, has shown that both the as-prepared and the HA-coated magnetite nanoparticles are superparamagnetic at T = 300 K, but the magnetization relaxation process is dominated by dipolar magnetic interactions of comparable strength. In the three samples, a collective frozen magnetic regime is established below T ∼ 20 K. These results indicate that the magnetite nanoparticles tend to form agglomerates in the as-prepared state, which are not substantially altered by the HA growth, coherently with the creation of electrostatic hydrogen bonds among the surface hydroxyl groups.

Single-molecule magnet of a tetranuclear dysprosium complex disturbed by a salen-type ligand and chloride counterions.

A series of three salen-type lanthanide complexes, e.g., [Dy4(L)2(HL)2Cl2(μ3-OH)2]2Cl2(OH)2·3CH3CH2OH·H2O (1) and [Ln4(L)2(HL)2Cl2(μ3-OH)2]Cl2·5CH3OH·4CH2Cl2 (Ln = Tb(III), 2; Ho(III), 3) have been isolated by the reactions of H2L (H2L = N,N'-bis(3-methoxysalicylidene)cyclohexane-1,2-diamine) with LnCl3·6H2O. X-ray crystallographic analysis reveals that all complexes 1-3 are isostructural, in which four Ln ions and eight O atoms form the distorted defective dicubane {Dy4O8} cores. Magnetic studies indicate that complex 1 exhibits two slow magnetic relaxation processes with effective energy barrier Ueff = 55.71 K under a zero direct-current field, which is attributed to the two coordination geometries of the Dy(III) ions with a salen-type ligand and coordination of a chloride counterion. It represents the highest energy barrier among the salen-type tetranuclear lanthanide single-molecule magnets.

Investigation on two magnon scattering processes in pulsed laser deposited epitaxial nickel zinc ferrite thin film

Ferromagnetic resonance (FMR) measurements are employed to evaluate the presence of the two magnon scattering contribution in the magnetic relaxation processes of the epitaxial nickel zinc ferrite thin films deposited using pulsed laser deposition (PLD) on the (0 0 1) MgAl2O4 substrate. Furthermore, the reciprocal space mapping reveals the presence of microstructural defects which acts as an origin for the two magnon scattering process in this thin film. The relevance of this scattering process is further discussed for understanding the higher FMR linewidth in the in-plane configuration compared to the out-of-plane configuration. FMR measurements also reveal the presence of competing uniaxial and cubic anisotropy in the studied films.

A nine-coordinated dysprosium(III) compound with an oxalate-bridged dysprosium(III) layer exhibiting two slow magnetic relaxation processes.

A 2D oxalate-bridged dysprosium(III) compound, formulated as [Dy(C2O4)1.5(H2O)3]n·2nH2O (1), has been hydrothermally isolated. As for compound 1, structural analysis reveals that the nine-coordinated Dy(III) ions reside in a slightly distorted tricapped trigonal prism. Under an applied magnetic field of 700 Oe, the compound was magnetically characterized as a new example that two slow relaxations of the magnetization processes can be observed in a 2D oxalate-bridged dysprosium(III) layer.

Cu(II)-Dy(III) and Co(III)-Dy(III) based single molecule magnets with multiple slow magnetic relaxation processes in the Cu(II)-Dy(III) complex.

Two dinuclear Schiff-base complexes [Cu(II)Dy(III)] and [Co(III)Dy(III)] have been synthesized and structurally characterized. The AC susceptibility measurements taken at BDC = 0.2 T show a slow magnetic relaxation typical for single-molecule magnets. Unusual is the presence of three relaxation branches in [Cu(II)Dy(III)]; the slowest (low-frequency) process possesses the barrier to spin reversal of U/kB = 2.8 K and an extrapolated relaxation time as slow as τ0 = 0.11 s. The intermediate-frequency process is typical for SMM of this class with U/kB = 122 K and τ0 = 9.9 × 10(-7) s; an onset of the high-frequency process is evidenced and this is the fastest. In contrast, the [Co(III)Dy(III)] complex free of exchange coupling exhibits only a single relaxation path with SMM parameters U/kB = 113 K and τ0 = 7.0 × 10(-9) s.

Effect of the helicity injection rate and the Lundquist number on spheromak sustainment

The dynamics of the magnetic relaxation process during the sustainment of spheromak configurations at different helicity injection rates is studied. The three-dimensional activity is recovered using time-dependent resistive magnetohydrodynamic simulations. A cylindrical flux conserver with concentric electrodes is used to model configurations driven by a magnetized coaxial gun. Magnetic helicity is injected by tangential boundary flows. Different regimes of sustainment are identified and characterized in terms of the safety factor profile. The spatial and temporal behavior of fluctuations is described. The dynamo action is shown to be in close agreement with existing experimental data. These results are relevant to the design and operation of helicity injected devices, as well as to basic understanding of the plasma relaxation mechanism in quasi-steady state.

Modulation of Magnetic Heating via Dipolar Magnetic Interactions in Monodisperse and Crystalline Iron Oxide Nanoparticles

In the pursuit of controlling the heat exposure mediated by magnetic nanoparticles, we provide new guidelines for tailoring magnetic relaxation processes via dipolar interactions. For this purpose, highly crystalline and monodisperse magnetic iron oxide nanocrystals whose sizes range from 7 to 22 nm were synthesized by thermal decomposition of iron organic precursors in 1-octadecene. The as-synthesized nanoparticles are soft nanomagnets, showing superparamagnetic-like behavior and SAR values which progressively increase with particle size, field frequency, and amplitude up to 3.6 kW/gFe. Our data show the influence of media viscosity, particle size, and concentration on dipolar interactions and consequently on the magnetic relaxation processes related to the heat release. Understanding the role of dipolar interactions is of great importance toward the use of iron oxide nanoparticles as efficient hyperthermia mediators.

Synthesis and magnetic properties of β-Ni(OH)2 and NiO nanosheets

In this report, we have synthesized hexagonal phase β-Ni(OH)2 nanosheets through a facile hydrothermal route. NiO nanosheets were obtained by thermal decomposition of the obtained β-Ni(OH)2 nanosheets at 450°C for 3h in air. The obtained samples were characterized by transmission electron microscopy (TEM), revealing that the obtained β-Ni(OH)2 and NiO nanosheets have the length and width of several decade nanometers. Thermogravimetric (TG) measurement showed that β-Ni(OH)2 nanosheets started to decompose at about 250°C with the major weight loss that happened between 270 and 323°C. The magnetic measurement results showed that β-Ni(OH)2 nanosheets have ferromagnetic behavior at 5K and paramagnetic behavior at 300K. NiO nanosheets exhibited an obvious hysteresis loops both at 5K and 300K due to the magnetization relaxation process. At the same time, the origin of magnetic properties of the obtained β-Ni(OH)2 and NiO nanosheets is discussed in detail.

Superparamagnetism in Cobalt Nanoparticles Coated by Protective Gold Layer

In this work we present the study on structural and magnetic properties of ne cobalt nanoparticles coated by protective gold layer synthetized by microemulsion method. Structural measurements (powder XRD, HRTEM) con rmed spherical shape of the particles, their nanocrystalline character and presence of individual Co and Au phases. Investigation of magnetic properties of the particles revealed superparamagnetic behavior at higher temperatures and magnetic hysteresis at low temperatures. Average magnetic moment of individual particle mp ∼ 86.3μB was established. The critical temperature, below which the magnetic moments of the particles are blocked, was TB = 6 K. Investigation of magnetic relaxation processes via magnetic susceptibility, detected one maximum attributed to single relaxation process, present in the particles. Obtained data, interpreted in terms of Neel-Arrhenius and Vogel-Fulcher theoretical models, con rmed the presence of strong magnetic interparticle interactions.

Large spin-relaxation barriers for the low-symmetry organolanthanide complexes [Cp*2 Ln(BPh4 )] (Cp*=pentamethylcyclopentadienyl; Ln=Tb, Dy).

Single-molecule magnets comprising one spin center represent a fundamental size limit for spin-based information storage. Such an application hinges upon the realization of molecules possessing substantial barriers to spin inversion. Axially symmetric complexes of lanthanides hold the most promise for this due to their inherently high magnetic anisotropies and low tunneling probabilities. Herein, we demonstrate that strikingly large spin reversal barriers of 216 and 331 cm(-1) can also be realized in low-symmetry lanthanide tetraphenylborate complexes of the type [Cp*2 Ln(BPh4 )] (Cp*=pentamethylcyclopentadienyl; Ln=Tb (1) and Dy (2)). The dysprosium congener showed hysteretic magnetization data up to 5.3 K. Further studies of the magnetic relaxation processes of 1 and 2 under applied dc fields and upon dilution within a matrix of [Cp*2 Y(BPh4 )] revealed considerable suppression of the tunneling pathway, emphasizing the strong influence of dipolar interactions on the low-temperature magnetization dynamics in these systems.

Microkelvin Thermometry with Bose–Einstein Condensates of Magnons and Applications to Studies of the AB Interface in Superfluid $$^3$$ 3 He

Coherent precession of trapped Bose–Einstein condensates of magnons is a sensitive probe for magnetic relaxation processes in superfluid $$^3$$ He-B down to the lowest achievable temperatures. We use the dependence of the relaxation rate on the density of thermal quasiparticles to implement thermometry in $$^3$$ He-B at temperatures below $$300\,\upmu $$ K. Unlike popular vibrating wire or quartz tuning fork based thermometers, magnon condensates allow for contactless temperature measurement and make possible an independent in situ determination of the residual zero-temperature relaxation provided by the radiation damping. We use this magnon-condensate-based thermometry to study the thermal impedance of the interface between A and B phases of superfluid $$^3$$ He. The magnon condensate is also a sensitive probe of the orbital order-parameter texture. This has allowed us to observe for the first time the non-thermal signature of the annihilation of two AB interfaces.

Hydroxide-Free Cubane-Shaped Tetranuclear [Ln4] Complexes

The reaction of the lanthanide(III) chloride salts [Gd(III), Tb(III), and Dy(III)] with a new chelating, flexible, and sterically unencumbered multisite coordinating compartmental Schiff-base ligand (E)-2-((6-(hydroxymethyl)pyridin-2-yl)methyleneamino)phenol (LH2) and pivalic acid (PivH) in the presence of triethylamine (Et3N) affords a series of tetranuclear Ln(III) coordination compounds, [Ln4(L)4(μ2-η(1)η(1)Piv)4]·xH2O·yCH3OH (1, Ln = Gd(III), x = 3, y = 6; 2, Ln = Tb(III), x = 6, y = 2; 3, Ln = Dy(III), x = 4, y = 6). X-ray diffraction studies reveal that the molecular structure contains a distorted cubane-like [Ln4(μ3-OR)4](+8) core, which is formed by the concerted coordination action of four dianionic L(2-) Schiff-base ligands. Each lanthanide ion is eight-coordinated (2N, 6O) to form a distorted-triangular dodecahedral geometry. Alternating current susceptibility measurements of complex 3 reveal frequency- and temperature-dependent two-step out-of-phase signals under zero direct current (dc) field, which is characteristic of single-molecule magnet behavior. Analysis of the dynamic magnetic data under an applied dc field of 1000 Oe to fully or partly suppress the quantum tunneling of magnetization relaxation process affords the anisotropic barriers and pre-exponential factors: Δ/kB = 73(2) K, τ0 = 4.4 × 10(-8) s; Δ/kB = 47.2(9) K, τ0 = 5.0 × 10(-7) s for the slow and fast relaxations, respectively.

A Cobalt Pyrenylnitronylnitroxide Single‐Chain Magnet with High Coercivity and Record Blocking Temperature

Coordination of a [Co(hfac)2] moiety (hfac = hexafluoroacetylacetonate) with a nitronylnitroxide radical linked to bulky, rigid pyrene (PyrNN) gives a helical 1:1 chain complex, in which both oxygen atoms of the radical NO(·) groups are bonded to Co(II) ions with strong antiferromagnetic exchange. The complex shows single-chain magnet (SCM) behavior with frequency-dependent magnetic susceptibility, field-cooled and zero-field-cooled susceptibility divergence with a high blocking temperature of around 14 K (a record among SCMs), and hysteresis with a very large coercivity of 32 kOe at 8 K. The magnetic behavior is partly related to good chain isolation induced by the large pyrene units. Two magnetic relaxation processes have been observed, a slower one attributable to longer, and a faster one attributable to short chains. No evidence of magnetic ordering has been found.

Investigation on intergranular exchange coupling effect in Pr9Fe85.5B5.5 ribbons

The intergranular exchange coupling effects are investigated via thermal activation of magnetization reversal in the magnetic relaxation process, combined with Henkel plots and the measurement of susceptibilities in three types of Pr9Fe85.5B5.5 ribbons. Exchange interaction between hard-hard grains is proposed in optimal melt-spun ribbons, as well as in over melt-spun ribbons even bearing a weak exchange coupling between soft-hard grains. In under melt-spun ribbons, the decoupled effect is proposed between hard-hard grains. These investigations may contribute to a clear understanding about the complicated nature of the intergranular exchange coupling in nanocomposite magnets.

A 2D → 2D polyrotaxane lanthanide–organic framework showing field-induced single-molecule magnet behaviour

An entangled Dy(iii) MOF with both polyrotaxane and polycatenane features was prepared, displaying two-step magnetic relaxation processes.

Controlling the Dipole–Dipole Interactions between Terbium(III) Phthalocyaninato Triple-Decker Moieties through Spatial Control Using a Fused Phthalocyaninato Ligand

Using a fused phthalocyaninato ligand to control the spatial arrangement of Tb(III) moieties in Tb(III) single-molecule magnets (SMMs), we could control the dipole-dipole interactions in the molecules and prepared the first tetranuclear Tb(III) SMM complex. [Tb(obPc)2]Tb(Fused-Pc)Tb[Tb(obPc)2] (abbreviated as [Tb4]; obPc = 2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato, Fused-Pc = bis{7(2),8(2),12(2),13(2),17(2),18(2)-hexabutoxytribenzo[g,l,q]-5,10,15,20-tetraazaporphirino}[b,e]benzenato). In direct-current magnetic susceptibility measurements, ferromagnetic interactions among the four Tb(3+) ions were observed. In [Tb4], there are two kinds of magnetic dipole-dipole interactions. One is strong interactions in the triple-decker moieties, which dominate the magnetic relaxations, and the other is the weak one through the fused phthalocyaninato (Pc) ligand linking the two triple-decker complexes. In other words, [Tb4] can be described as a weakly ferromagnetically coupled dimer of triple-decker Tb2(obPc)3 complexes with strong dipole-dipole interactions in the triple-decker moieties and weak ones through the fused phthalocyaninato ligand linking the two triple-decker complexes. For [Tb4], dual magnetic relaxation processes were observed similar to other dinuclear Tb(III)Pc complexes. The relaxation processes are due to the anisotropic centers. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Tb(3+) ions in the systems. Through a better understanding of the magnetic dipole-dipole interactions obtained in these studies, we have developed a new strategy for preparing Tb(III) SMMs. Our work shows that the SMM properties can be fine-tuned by introducing weak intermolecular magnetic interactions in a controlled SMM spatial arrangement.

Structural and Magnetic Studies of a New Co(II) Thiocyanato Coordination Polymer Showing Slow Magnetic Relaxations and a Metamagnetic Transition

Reaction of Co(NCS)2 with 4-ethylpyridine leads to the formation of three new compounds of composition Co(NCS)2(4-ethylpyridine)4 (1), [(Co(NCS)2]2(4-ethylpyridine)6 (2), and [Co(NCS)2(4-ethylpyridine)2]n (3). In all compounds the coordination of the Co(II) ions is distorted octahedral. 1 consists of discrete monomeric complexes and in 2 two Co(II) cations are linked by pairs of μ-1,3-bridging thiocyanato ligands into dimers. In the crystal structure of 3 the Co(II) cations are connected into chains by the same bridge as in 2. Magnetic studies show that 1 and 2 are paramagnets down to a temperature of 2 K, while compound 3, which is the main object of this study, is an antiferromagnet with the Néel temperature T(N) = 3.4 K. Its magnetic structure is built from ferromagnetic chains, which are weakly antiferromagnetically coupled. With increasing magnetic field a metamagnetic transition starts at ~175 Oe, as observed for a polycrystalline sample. Magnetic relaxations, which were observed in the antiferromagnetic state, are retained at the metamagnetic transition. With decreasing field 3 remains in a state, in which except of the faster magnetic relaxation process in single chains also a slower process coexists resulting in the appearance of a magnetic hysteresis loop.

Ferromagnetic resonance study of structure and relaxation of magnetization in NiFe/Ru superlattices

The structural properties and relaxation processes of magnetization in [Ni81Fe19(t1)/Ru(t2)]N superlattices (N=number of bilayers) were analyzed by ferromagnetic resonance (FMR) with a fixed microwave frequency. One series of samples was deposited with constant NiFe layer thickness (t1) and variable Ru layer thickness (t2); the other series, with constant t2 and variable t1. A single FMR mode was observed for t2<15Å and t1>75Å and it has been attributed to the resonance of the exchange-coupled NiFe layers across the Ru interlayers. For the other values of t1 and t2, several FMR modes appeared and they were associated to non-coupled magnetic phases with different effective magnetization formed during the multilayer growth. The FMR linewidths were analyzed as a function of the magnetic layer thickness and a strong dependence on t1−2 was observed. It was attributed to the contribution of the two-magnon scattering mechanism for the linewidth.

Influence of Intramolecular f-f Interactions on Nuclear Spin Driven Quantum Tunneling of Magnetizations in Quadruple-Decker Phthalocyanine Complexes Containing Two Terbium or Dysprosium Magnetic Centers

Nuclear spin driven quantum tunneling of magnetization (QTM) phenomena, which arise from admixture of more than two orthogonal electronic spin wave functions through the couplings with those of the nuclear spins, are one of the important magnetic relaxation processes in lanthanide single molecule magnets (SMMs) in the low temperature range. Although recent experimental studies have indicated that the presence of the intramolecular f-f interactions affects their magnetic relaxation processes, little attention has been given to their mechanisms and, to the best of our knowledge, no rational theoretical models have been proposed for the interpretations of how the nuclear spin driven QTMs are influenced by the f-f interactions. Since quadruple-decker phthalocyanine complexes with two terbium or dysprosium ions as the magnetic centers show moderate f-f interactions, these are appropriate to investigate the influence of the f-f interactions on the dynamic magnetic relaxation processes. In the present paper, a theoretical model including ligand field (LF) potentials, hyperfine, nuclear quadrupole, magnetic dipolar, and the Zeeman interactions has been constructed to understand the roles of the nuclear spins for the QTM processes, and the resultant Zeeman plots are obtained. The ac susceptibility measurements of the magnetically diluted quadruple-decker monoterbium and diterbium phthalocyanine complexes, [Tb-Y] and [Tb-Tb], have indicated that the presence of the f-f interactions suppresses the QTMs in the absence of the external magnetic field (H(dc)) being consistent with previous reports. On the contrary, the faster magnetic relaxation processes are observed for [Tb-Tb] than [Tb-Y] at H(dc) = 1000 Oe, clearly demonstrating that the QTMs are rather enhanced in the presence of the external magnetic field. Based on the calculated Zeeman diagrams, these observations can be attributed to the enhanced nuclear spin driven QTMs for [Tb-Tb]. At the H(dc) higher than 2000 Oe, the magnetic relaxations become faster with increasing Hdc for both complexes, which are possibly ascribed to the enhanced direct processes. The results on the dysprosium complexes are also discussed as the example of a Kramers system.

Two tetranuclear 3d–4f complexes: Syntheses, structures and magnetic properties

Abstract The solvothermal reactions of 3,5-bis(trifluoromethyl)benzoic acid (HL) and 2,2′-bipyridine (bipy) with the corresponding metal salts afforded two novel 3d–4f tetranuclear complexes M2Dy2(L)10(bipy)2 (M = Mn 1, Cu 2), which have been characterized by single-crystal X-ray diffraction, infrared spectroscopy, element analyses, powder X-ray diffraction and thermal gravimetric analyses. Complexes 1 crystallizes in the triclinic space group P-1, and the completely deprotonated L ligands possess μ2: η1, η1 and μ2: η2, η1 coordination modes to bridge adjacent metal ions which further connect into 2D layers by hydrogen bonds. Complex 2 crystallizes in the distinct monoclinic space group P21/c, and adjacent metal ions were linked by L ligands with the same coordinated patterns with 1, and supramolecular sheets were formed in the ab plane. Dynamic magnetic susceptibility studies reveal slow magnetic relaxation processes for 2, suggesting SMM type behavior.