Unusual magnetic relaxation in a single-molecule magnet with toroidal magnetic moments

We report the synthesis and characterization of a single-molecule magnet composed of triangular clusters of dysprosium ions.The structural study shows that the symmetry changes from one polar point group(mm2)at room temperature to another polar point group(m)at low temperature.Magnetic studies and theory calculations illustrate that the vortex distribution of magnetic dipoles in the triangular dysprosium clusters forms a toroidal magnetic moment.Interestingly,the analysis of AC magnetic susceptibility reveals the coexistence of three distinct magnetic relaxation processes,corresponding to the Raman,Orbach,and QTM relaxation pathways,respectively.The sum of three modified Debye functions is successfully used to describe the multiple relaxation behavior.

AN IMPROVED MODEL FOR COMPUTING SOLUTION DYNAMICS OF NATURAL PRODUCTS WITH ^(13)C NUCLEAR MAGNETIC RELAXATION

The fully anisotropic molecular overall tumbling model with methyl conformation jumps internal rotation among three equivalent sites is proposed,the overall tumbling rotation rates and the methyl internal rotation rates of ponicidin are computed with this model from ~C relaxation parameters.

Measurement of Magnetization Curve and Magnetic Relaxation for 2H-NbSe_2 Crystals

The characteristics of electronic transport properties: behaviors of magnetization curve and magnetic relaxation of a typical normal superconductor 2H?NbSe2 are investigated. The results show thatT c and ΔT c of the samples are 7. 2, 0. 18 K, indicating that superconducting energy gap at zero temperature is 1. 1. meV. No fish tail shape is found in the magnetization curves at several temperatures. The relationship between remnant magnetic moment and time reveals that the magnetic flux creep of the sample agrees with the Kim-Anderson thermal activation model with the relaxation rateS=0.00036 atT=6 K. Key words magnetization curve - magnetic relaxation - flux pinning CLC number O 511+. 4 Foundation item: Supported by the National Natural Science Foundation of China (10174056)Biography: Zhang Ning (1978-), male, Master candidate, reseach direction: high temperature superconductor.

Syntheses of new di-nuclear and tetra-nuclear lanthanide 9-anthracenecarboxylates:Magnetocaloric effect,slow magnetic relaxation and luminescent properties

Lanthanide complex-based materials with magnetic and luminescent properties have received a great deal of attention,owing to their importantly potential applications in diverse fields.In this work,the 9-anthracenecarboxylic acid(9-Haca)as bridging ligand was applied in combination with optically activeπ-conjugated 2,4,6-tri(2-pyridyl)-1,3,5-triazine(tptz)to construct a series of new di-nuclear and tetranuclear lanthanide 9-anthracenecarboxylates[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]·0.25H_(2)O(1),[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]·0.5AQ·CH_(3)COOH_(2)H_(2)O[Ln=Sm(2a),Eu(2b),Gd(2c),Tb(2d),Dy(2e),Tm(2f);AQ=9,10-anthracenedione]and[Ln_(4)(9-aca)_(10)(tptz)_(2)(CH3COO)2]·H_(2)O[Ln=Eu(3a),Gd(3b),Dy(3c)].1 displays a di-nuclear centrosymmetric moiety[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]built up from two complex[La(9-aca)_(2)(tptz)]groups bridged by one H_(2)O molecule and two syn-syn-μ2-η1:η1-9-aca-bridging ligands,while 2a-2f are isostructural and co mprise another di-nuclear centrosymmetric moieties[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]based on two complex[Ln(9-aca)_(2)(tptz)(H_(2)O)]groups connected by two syn-syn-μ2-η1:η1-9-aca-bridging ligands,3a-3c are isostructural and show tetra-nuclear centro symmetric moieties[Ln4(9-aca)10(tptz)2(CH3COO)2]containing three types of coordination modes of 9-aca-ligands.The present compounds offer the only examples of lanthanide 9-anthracenecarboxylates decorated by optically active tptz.Magnetic investigations of 2a,2c-2f,and 3b-3c indicate that 3c is typical of slow relaxation of the magnetization,while 2c and 3b show significant magnetocaloric effect(MCE)with the value of-ΔSm of 5.26 J/(kg·K)at 4 K and 15.65 J/(kg·K)at 2 K(ΔH=7 T),respectively.The luminescent properties were also studied and reveal that the characteristic luminescent properties of the 7r-conjugated aromatic ligands are introduced into magnetic lanthanide 9-anthracenecarboxylates,simultaneously exhibiting slow magnetic relaxation(or MCE)and luminescent properties.

Slow magnetic relaxation in a 3D dysprosium(Ⅲ)-fluoro-oxalate framework containing zig-zag [Dy-F]n chains

Dysprosium complexes based on [F-Dy] or near-linear [F-Dy-F] unit are of great concern in the field of single-molecule magnets due to their large magnetic anisotropy.Here,the crystal structure and the magnetic relaxation dynamics were reported for a three-dimensional(3 D) metal-organic framework(MOF):[DyF(C_(2)O_(4))(H_(2)O)2]n·2nH_(2)O(1),which is the unique MOF containing zig-zag [Dy-F]_(n) chains.Magnetic susceptibility characterization reveals that 1 is one of the few 3 D MOFs which show slow magnetic relaxation under zero dc field.And the effective energy barrier of 72 K for 1 is also higher than most Dy-based 3 D MOFs.The diamagnetic ion dilution study shows that the ferromagnetic exchange couplings mainly transmitted by F^(-) bridges in 1 contribute little to the energy barrier,but effectively suppress the quantum tunneling process and result in a smooth hysteresis loop with no waist-restricted step.

Structures and magnetic relaxation properties of cyclopentadienyl/β-diketonate/trispyrazolylborate hybridized dysprosium single-molecule magnets

The combination of cyclopentadiene,β-diketonate and tripyrazoylborate ligands with dysprosium ion afforded five mononuclear compounds:[(Cp)2Dy(Tp∗)](1Dy),[(Cp)Dy(Tp∗)Cl(THF)](2Dy),[(Cp)Dy(Tp)Cl(THF)](3Dy),[(DBM)Dy(Tp)Cl(THF)](4Dy),[{(Tp)Dy(DBM)_(2)(H_(2)O)}·THF](5Dy)(Cp=cyclopentadiene;Tp∗=hydrotris(3,5-dimethyl-1-pyrazolyl)borate;Tp=hydrotris(1-pyrazolyl)borate;DBM=dibenzoylmethanoate).Magnetic study revealed that 1Dy and 3Dy exhibited typical butterfly-type hysteresis.AC susceptibility study combined with ab initio calculations indicated that the magnetic relaxation behaviors of 1Dy–4Dy were governed by the Orbach and Raman processes under applied DC field.Moreover,3Dy showed two-step magnetic relaxation,which was attributed to the static disordering of the coordinated THF molecule.Magnetic anisotropy analysis indicated that it was the relative strength of the interactions between DyIII and surrounding ligands that determined the orientation of the magnetic easy axis.

Two temperature-dependent 2D heterometallic Cd(Ⅱ)-Dy(Ⅲ)coordination polymers exhibiting slow magnetic relaxation and luminescence properties

Two unique two-dimensional(2D)Cd(Ⅱ)-Dy(Ⅲ)heterometallic coordination polymers,{[DyCd(HPMA)(PMA)_(2)(H_(2)O)_(4)]·2H_(2)O}_n(1)and[DyCd(PAA)(PMA)_(2)(H_(2)O)_(3)]_(n)(2,PAA^(-)=phenylacetate),were prepared successfully based on the phenylmalonic acid(H_(2)PMA).The construction of two polymers is sensitive to the reaction temperature and can be synthesized directionally at room temperature and 90℃,respectively.Complexes 1 and 2 display 2D layer structures that include dinuclear[Dy_(2)]cluster node and Dy(Ⅲ)-based 1D zigzag chain motif severally.The Dy(Ⅲ)-based units in two structures both are spaced well with the adjacent ones by the diamagnetic Cd(Ⅱ)-based moieties.The magnetic studies reveal that 1 and 2both display slow magnetic relaxation with temperature-dependent relaxation peaks producing an effective energy barrier(Δτ)of 74.5 and 32.1 K,separately.Furthermore,the solid-state photophysical properties of 1 and 2 show strong characteristic luminescent emissions of Dy(Ⅲ)ion in the visible region.

Magnetocaloric effect and slow magnetic relaxation behavior in binuclear rare earth based RE_(2)(L)_(2)(DMF)4(RE=Gd,Tb,and Dy) complexes

Three binuclear rare earth based complexes combining RE ions with semirigid tricarboxylic ligand(H_(3)L).namely,[RE_(2)(L)_(2)(DMF)_(4)][RE=Gd,Tb,and Dy;H_(3)L=5-((4-Carboxybenzyl)oxy)isophthalic acid;DMF=N,N-dimethylformamide]complexes,were fabricated success fully.The RE_(2)(L)_(2)(DMF)_(4) co mplexe s consist of two central RE ions with the same coordination environment which were connected by two tridentate bridging carboxylic groups and two syn-syn bidentate bridging carboxylic groups originating from the L^(3-)ligands to form the{RE_(2)}dimeric unit,and thus provides the basis for further constructing a dense three-dimensional(3 D)network structure.Moreover,the present RE_(2)(L)_(2)(DMF)_(4) complexes can be described by a topology diagram with the topology point symbol of{4^(2)·6}_(2){4^(4)·6^(2)·8^(7)·10^(2)}.Weak antiferromagnetic(AFM)coupling between the adjacent RE ions for all the present complexes was found according to the magnetic calculations.The observed significant cryogenic magnetocaloric effect(MCE)with the maximum magnetic entropy change-ΔS_(M)^(max) to be 26.3 J/(kg·K)withΔH=7 T in Gd_(2)(L)_(2)(DMF)_(4) complex makes it competitive for the cryogenic magnetic refrigerant.Moreover,the slow magnetic relaxation behavior at 0.2 T dc field with an obvious large U_(eff)/k=45(4)K and τ_(0)=6.5(2)×10^(-10)s was confirmed in Dy_(2)(L)_(2)(DMF)_(4)complex.This work not only provides an effective strategy for obtaining molecular materials with high MCE,but also confirms that tricarboxylate ligands are the ideal choice for constructing stable high dimensional geometric structures.

Synthesis of two lanthanide clusters Ln^(Ⅲ)_(4)(Gd_(4) and Dy_(4)) with [2×2] square grid shape:Magnetocaloric effect and slow magnetic relaxation behaviors

Two isostructural tetranuclear lanthanide clusters named [Ln_(4)(L)_(4)(CH_(3) O)_(4)]·CH_(3) OH(Ln=Gd(Ⅲ) for 1,Dy(Ⅲ) for 2,H_(2) L=N’-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide) were successfully isolated by using a polydentate Schiff based ligand and Ln(Ⅲ) nitrate salts.The structures of 1 and 2 were characterized by X-ray structural analyses,they are held by four double deprotonated ligands L2-.In them all the lanthanide ions are eight-coordinated and distributed over four vertices of a parallelogram,presenting a Ln4 cluster with a strict [2 × 2] square grid pattern.The details of magnetic analysis show that 1 displays weak anti-ferromagnetic exchange between neighboring Gd(Ⅲ) ions through carboxylate oxygen and methanol oxygen ligand atoms.Furthermore,1 exhibits significant magnetocaloric effect with the maximum entropy change-ΔSm value of 28.5 J/(kg K) for ΔH=7.0 T at 2.0 K.For compound 2,remarkable slow magnetic relaxation behaviors are observed in the presence of zero magnetic field with τ0=1.02 × 10^(-6) s and energy barrier ΔE/kB=43.24 K.

Two lanthanide(Ⅲ)-copper(Ⅱ) chains based on[Cu_2Ln_2]clusters exhibiting high stability,magnetocaloric effect and slow magnetic relaxation

Two 3d-4f heterometallic one-dimensional chains with neutral 4,4＇-bipyridine ligands as linkers and[Cu2Ln2] clusters （Ln = Gd for 1, Dy for 2） as nodes have been hydrothermally synthesized and structurally characterized. Magnetic studies indicate that complex 1 exhibits a relatively large magnetocaloric effect, with an entropy change -△Smax m= 24.8 J kg 1 K^-1, whilst, complex 2 features slow magnetic relaxation at low temperature.

Magnetic relaxation behavior of a spatially closed dysprosium(Ⅲ) phthalocyaninato double-decker complex

The SMM properties of the spatially closed Dy（Ⅲ） double-decker Pc complex Dy（obPc）2 （1）, which is equivalent to a pseudo dinuclear complex, are reported. Complex 1 crystallized with ethanol in the crystal lattice in the monoclinic space group P22/n and was isomorphous with Tb（obPc）2 （3）, which is arranged in a dimer structure along the b axis. The intermetallic Dy-Dy distance was determined to be 0.756 nm. ZMT versus T plots for 1 decreased with a decrease in T, which suggests the existence of an antiferromagnetic （AF） interaction between the Dy3＋ ions. The M-H curve for 1 at 1.8 K showed magnetic hysteresis. In ac susceptibility measurements on a powder sample of 1, which were dependent on the applied ac field, indicating that 1 is an single molecule magnet （SMM）, a maximum appeared at 22 K at an ac frequency 09 of 1488 Hz. The shape of the peaks dras- tically changed, and the peaks did not shift when an Hd~ large enough to suppress the quantum tunneling of the magnetization （QTM） was applied. The energy barrier （A/hc） was estimated to be 44 cm-1 with a pre-exponential factor （r0） of 1.6 × 10-5 s from an Arrhenius plot. Our results suggest that the SMM/magnetic properties of 1 significantly change in a dc magnetic field. These relaxation mechanisms are related to the energy gap of the ground state and to QTM.

Static field induced magnetic relaxations in dinuclear lanthanide compounds of [phen_2Ln_2(HCOO)_4(HCOO)_(2-2x)(NO_3)_(2x)](1,Ln=Gd and x=0.52; 2, Ln=Er and x=0.90; phen=1,10-phenanthroline)

Two dinuclear lanthanide (Ln) complexes, formulated as [phen2Ln2(HCOO)4(HCOO)2 2x(NO3)2x] (1, Ln = Gd and x = 0.52; 2, Ln = Er and x = 0.90; phen = 1,10-phenanthroline), were synthesized and characterized. They are isostructural. The dinuclear molecule consists of two Ln3+ bridged by four formate groups and chelated by phen and formate/nitrate ligands, and the Ln3+ possesses a coordination environment of distorted tri-capped trigonal prism of LnOTN2. Both compounds behave as paramag- nets between 2 and 300 K, but display two static field induced magnetic relaxation processes. One is slow and of spin-lattice type, and it results from the lifting of Kramer's degeneracy of the ground-states of both Gd3+ and Er3+, and the other is fast, and it might be spin-spin type.

Dramatic Impact of Auxiliary Ligands on the Dynamic Magnetic Relaxation in Tetranuclear Dy^(III)_(2)Zn^(II)_(2) Single Molecule Magnets

Better understanding the determining factors of dynamic magnetic relaxation in polynuclear lanthanide based single-molecule magnets(SMMs)remains a challenge due to the complexity of such architectures involving interactions between the magnetic centers.To address this issue,two structurally related heterometal Dy^(III)_(2)Zn^(II)_(2) SMMs,[Zn_(2)Dy_(2)(L)_(4)(Ac)_(2)(DMF)(CH_(3)OH)]·CH_(3)OH·2H_(2)O(1)and[Zn_(2)Dy_(2)(L)_(4)(Ac)_(2)(DMF)_(2)]·4CH_(3)CN(2)(H_(2)L=(E)-2-((2-hydroxy-3-methoxybenzylidene)amino)-4-methyphenol,DMF=N,N-dimethylformamide),are introduced and investigated.Through modifying the auxiliary ligands on one Dy^(III) site while retaining that on the other Dy^(III),the intramolecular magnetic interactions and relaxation dynamics in these two heterometallic-Dy^(III)_(2)Zn^(II)_(2) SMMs can be tuned,demonstrating a dramatic change in the magnet relaxation behavior with energy barrier changing from a negligible value for 1 to 305 K for 2.Ab initio calculations reveal that changing the coordination geometries on the Dy^(III) sites can significantly affect the magnetic interactions as well as single-ion anisotropy.

Fe^(2+)/Fe^(3+)Conversation-Mediated Magnetic Relaxation Switching for Detecting Staphylococcus Aureus in Blood and Abscess via Liposome Assisted Amplification

Rapid and accurate detection of pathogenic bacteria of Staphylococcus aureus(S.aureus)is of importance in the fi eld of clinical research and practical application.Herein,we report a magnetic relaxation switching(MRS)-based strategy for detecting S.aureus in complex samples via the assistance of signal amplifi cation system of liposome.In this design,vancomycin(Van)modifi ed 200 nm magnetic beads(MB_(200)-Van)and biotinylated immunoglobulin(Biotin-IgG)were employed as capture probes for S.aureus which following labelled by biotinylated liposomes loading with glucose molecule(Biotinliposome@Glu,BLGs)based on the affi nity of biotin with streptavidin.The released glucose molecules combining with glucose oxidase generated Fe^(3+),causing transverse relaxation time(T_(2))signal change.The combination of dual recognition of S.aureus,liposome assisted signal amplifi cation,and the MRS-based assay achieved direct and specifi c detection of S.aureus in blood and abscess samples.The as-proposed method for S.aureus assay in this study shows potential application for infectious diagnosis in clinical.

Tuning Magnetic Relaxation in Square-Pyramidal Dysprosium Single-Molecule Magnets Using Apical Alkoxide Ligands

Eight square-pyramidal dysprosium complexes of the type[Dy(X)(DBP)_(2){TMG(H)}_(2)]were synthesized,where TMG(H)denotes 1,1,3,3-tetramethylguanidine,X denotes an alkoxide ligand or anionic guanidinate in the apical position,and DBP denotes 2,6-di-tert-butylphenoxide.These complexes,expressed as 5-Dy-X,are single-molecule magnets(SMMs)with properties dependent on the nature of the apical X ligand.

Stepwise assembly of heterometallic 3d–4f chain exhibiting slow magnetic relaxation

The self-assembly of polyalcohol ligand 1,1,1-tris（hydroxymethyl）ethane with Dy（NO3）3· 6H2 O and Cr3O-Bzo-t-Bu precursor in the presence of triethylamine step-by-step generated a heterometallic 3d–4f chain. Magnetic investigation of the complex indicates typical slow relaxation of the magnetization at low temperature.

3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation

A 3D mixed-valence Co（Ⅲ）-Co（Ⅱ） compound [Co9（bta）10（Hbta）2（H2O）10]n·[22（H2O）]n （1） （H2bta=N,N-bis（1H-tetrazole-5- yl）-amine） was hydrothermally synthesized by reaction of Co（NO3）2·6H2O with H2bta·H2O. Compound 1 consists of three kinds of distorted-octahedral [CoⅡ（N4O2）] paramagnetic nodes which are separated by [CoⅢ（bta）2（Hbta）]2-/[CoⅢ（bta）3]3- dia- magnetic linkers to generate a 3D porous metal-organic framework （MOF） with alternative …Co（Ⅲ）…Co（II）… array and channels incorporating water molecules. Under an applied magnetic field of 4000 Oe, compound 1 exhibits slow relaxation of magnetization at low temperatures, giving AE/kB=30.O0 K and ι0=2.0×10^-8 s.

Interfacial DMI in Fe/Pt thin films grown on different buffer layers

We study the interfacial Dzyaloshinskii-Moriya interactions(i-DMI)of Fe/Pt bilayers grown on Si substrates with MgO,SiO_(2),or Ta each as a buffer layer on the basis of wave-vector-resolved Brillouin light scattering(BLS)measurement.The obtained i-DMI energy values for Fe/Pt on MgO,Ta,and SiO_(2) buffer layers are 0.359,0.321,and 0.274 mJ/m~2,respectively.The large i-DMI value observed in Fe/Pt system on the MgO buffer layer can be attributed to the good interfacial quality and the Rshaba effect at the MgO/Fe interface.Moreover,the MgO/Fe/Pt system,benefiting from better sample quality,exhibits a lower damping factor.Furthermore,layer-resolved first-principles calculations are carried out to gain a more in-depth understanding of the origin of the i-DMI in the Fe/Pt system.The results indicate that in the Fe(110)/Pt(111)system,the substantial DMI energy between Fe spins at the interface is related to a significant change in spin-orbit coupling(SOC)energy in the neighboring Pt layer.In contrast,for the MgO(002)/Fe(002)system,both the DMI and its related SOC energy are concentrated at the interfacial Fe layer.Our investigation will provide a valuable insight into the spintronic community in exploring novel devices with chirality dependence.

Effect of interface magnetization depinning on the frequency shift of ferromagnetic and spin wave resonance in YIG/GGG films

Nowadays the yttrium iron garnet(Y3Fe5O12, YIG) films are widely used in the microwave and spin wave devices due to their low damping constant and long propagation distance for spin waves. However, the performances, especially the frequency stability, are seriously affected by the relaxation of the interface magnetic moments. In this study, the effect of out-of-plane magnetization depinning on the resonance frequency shift(△ fr) was investigated for 3-μm YIG films grown on Gd3Ga5O12(GGG)(111) substrates by liquid-phase epitaxy. It is revealed that the ferromagnetic resonance(FMR) and spin wave propagation exhibit a very slow relaxation with relaxation time τ even longer than one hour under an out-of-plane external magnetic bias field. The △ fr span of 15.15–24.70 MHz is observed in out-of-plane FMR and forward volume spin waves. Moreover, the △ fr and τ depend on the magnetic field. The △ fr can be attributed to that the magnetic moments break away from the pinning layer at the YIG/GGG interface. The thickness of the pinning layer is estimated to be about9.48 nm to 15.46 nm according to the frequency shifting. These results indicate that △ fr caused by the pinning layer should be addressed in the design of microwave and spin wave devices, especially in the transverse magnetic components.

A Simulation Study on the Specific Loss Power in Magnetic Hyperthermia in the Presence of a Static Magnetic Field

Our purpose in this study was to present a method for estimating the specific loss power (SLP) in magnetic hyperthermia in the presence of an external static magnetic field (SMF) and to investigate the SLP values estimated by this method under various diameters (D) of magnetic nanoparticles (MNPs) and amplitudes (H0) and frequencies (f) of an alternating magnetic field (AMF). In our method, the SLP was calculated by solving the magnetization relaxation equation of Shliomis numerically, in which the magnetic field strength at time t (H(t)) was assumed to be given by , with Hs being the strength of the SMF. We also investigated the SLP values in the case when the SMF with a field-free point (FFP) generated by two solenoid coils was used. The SLP value in the quasi steady state (SLPqss) decreased with increasing Hs. The plot of the SLPqss values against the position from the FFP became narrow as the gradient strength of the SMF (Gs) increased. Conversely, it became broad as Gs decreased. These results suggest that the temperature rise and the area of local heating in magnetic hyperthermia can be controlled by varying the Hs and Gs values, respectively. In conclusion, our method will be useful for estimating the SLP in the presence of both the AMF and SMF and for designing an effective local heating system for magnetic hyperthermia in order to reduce the risk of overheating surrounding healthy tissues.