Structural fine-tuning is of significant importance to enhance the magnetic anisotropy and elucidate the magneto-structural relationship for single molecule magnets(SMMs).For this purpose,two mononuclear Dy^(3+) SMMs:...Structural fine-tuning is of significant importance to enhance the magnetic anisotropy and elucidate the magneto-structural relationship for single molecule magnets(SMMs).For this purpose,two mononuclear Dy^(3+) SMMs:[Dy{HB(pz)3}2(Sal)](1) and [Dy{HB(pz)_(3)}_(2)(MeO-Sal)](2),where HB(pz)_(3)^(-)represents hydro tris(pyrazolyl)borate,Sal denotes salicyiaidehyde and MeO-Sal stands for 5-methoxysalicylaldehyde,were designed and synthesized.Single crystal X-ray diffraction tests show that the two SMMs have very similar eight-coordinated molecule structures,although the introducing of-MeO substituent on salicyiaidehyde ligand induces the changes on the molecule packing mode and the space group.Both the two SMMs have a Dy-O_(aryloxidebond) that is significantly shorter than other Dy-O/N bonds,which defines the orientation of main anisotropy axis of the ground Kramers doublets and engenders the slow relaxation of the magnetization behavior,as evidenced by the magnetic susceptibility and the ab initio calculation.Though with an electron-donating substituent on the axial Sal ligand in 2,the collective magnetic anisotropy is not enhanced and the corresponding magneto-structural relationship is discussed based on the experimental and theoretical calculation results.In addition,as neutral molecules,1 and 2 are soluble in several common organic solvents,like CH_(2)Cl_(2),CHCl_(3),THF and so on.展开更多
Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=P...Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=Pamoic acid, DMA=dimethylacetamide, DMF=N,N-dimethylformamide）, have been synthesized by the reaction of Ln（NO3）a-6H20 with pamoic acid through layer diffusion method. These complexes were characterized by single crystal X-ray diffraction, infrared spectroscopy （IR）, thermogravimetric analysis （TGA）, fluorescence and magnetic measurements. Solvents and lanthanide atoms in the reaction play an important role in controlling different structures. Type I demonstrated 1-D linear chain structure connected by Ln atoms and PA ligands. Type II exhibited non-interpenetrating 3-D 6-connected 43612 nets based on binuclear [Ln2（CO2）6（DMF）4] cores. Magnetic properties of complexes 1-4 were investigated in details. Complex 1 shows significant magnetocaloric effect with -△Sm=20.37 J kg^-1 K^-1 at 3.0 K and 7 T. Complex 2 exhibits slow relaxation of the magnetization. Complexes 3-6 exhibit both ligand- and metal-centered fluorescent properties. Complex 6 demonstrates fluorescent sensing of DMF and Cu^2＋ ion.展开更多
Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2...Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2·15H_(2)O(3)and{Co(H_(2)O)2[Ir(ppyCOO)_(2)(bpy)]_(2)}·2CH_(3)OH·3H_(2)O(4),have been synthe-sized by combining paramagnetic Co^(Ⅱ)ion with luminescent Ir^(Ⅲ)-metalloligand,[Ir(ppyCOOH)_(2)(bpy)][Ir(ppyCOO)_(2)(bpy)]·5H_(2)O(1),where ppyCOOH=3-(pyridin-2-yl)benzoic acid and bpy=2,2'-bipyridyl.Owing to the variable charged states of compound 1 at dif-ferent pH,compounds 2 and 3 are discrete ionic complexes containing hydrated Co^(2+)cations and deprotonated[Ir(ppyCOO)_(2)(bpy)]-anions as well as coexisting neutral[Ir(ppyCOO)(ppyCOOH)(bpy)](for 2)or Co(H_(2)O)_(4)[Ir(ppyCOO)_(2)(bpy)]_(2) trinuclear molecule(for 3).Whereas compound 4 consists of self-assembled two-dimensional coordination polymer with Co-metalloligand dative bonds.The hexa-coordinated Co^(Ⅱ)cores in all complexes display octahedral geometries with varying degrees of distortion.In a bias dc field,the ac susceptibilities for 2-4 reveal slow magnetic relaxation.Moreover,the solid-state phosphorescence is observed for compounds 2 and 3 due to weak supramolecular interaction between Co^(Ⅱ)ion and Ir-moiety but is severely quenched for 4,where the Co center is strongly connected to the metalloligand.To the best of our knowledge,this is the first report of Ir-Co systems showing both slow magnetization relaxation and photoluminescence.展开更多
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 andΔT c of the sam...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 andΔT 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.展开更多
Two CoⅡ-based complexes,{[Co(dps)_(2)(N_(3))_(2)]·H_(2)O}_n(1)and[Co(dps)_(2)(N_(3))_(2)]_n(2),show a 1D chain and a 3D network,respectively.The central CoⅡions in the complexes have the same coordination envir...Two CoⅡ-based complexes,{[Co(dps)_(2)(N_(3))_(2)]·H_(2)O}_n(1)and[Co(dps)_(2)(N_(3))_(2)]_n(2),show a 1D chain and a 3D network,respectively.The central CoⅡions in the complexes have the same coordination environment with the[Co(dps)_(4)(N_(3))_(2)]unit.Although the differences in crystal parameters are nearly negligible,their magnetic properties are very different.AC susceptibility data show that 1 behaves as a typical field-induced single-ion magnet(SIM)with the out-of-phase(χ_(M)”)signals,while 2 shows ac signals ofχ_(M)”without peaks even under applied dc filed within our measurement window.Far-IR magneto-spectra(FIRMS)show strong spin-phonon couplings at 0 T in 2,likely making the magnetic relaxation in 2 fast,while the couplings are negligible in 1.Small spin-phonon coupling in 1 likely leads to slower magnetic relaxation,making 1 a SIM.The difference in the properties is due to the structural rigidity of 2 in its 3D network,leading to stronger spin-phonon coupling.Combined high-field EPR(HF-EPR)and FIRMS studies give spin-Hamiltonian parameters,including D=64.0(9)cm^(-1),|E|=15.7(2)cm^(-1)for 1 and D=80.0(2)cm^(-1),|E|=19.0(1)cm^(-1)for 2.展开更多
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, e...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.展开更多
The quantum tunnelling of magnetization （QTM） in single crystals of the single molecule magnet （Mn1-xCrx）12- Ac （x=0, 0.03, 0.04, 0.05） has been investigated. In comparison with its parent Mnl2-Ac, a greater rat...The quantum tunnelling of magnetization （QTM） in single crystals of the single molecule magnet （Mn1-xCrx）12- Ac （x=0, 0.03, 0.04, 0.05） has been investigated. In comparison with its parent Mnl2-Ac, a greater rate of magnetization relaxation and a lower effective potential-energy barrier have been observed in Cr-doping samples. This modulation of QTM due to the Cr-doping could be attributed to the small change of Sz due to the smaller spin of Cr itself and additional intrinsic but distributed transverse and longitudinal anisotropy raised by a subtle change of the local environment in the magnetic Mn12 core.展开更多
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-dimethyl...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.展开更多
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...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.展开更多
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 succe...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.展开更多
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 characte...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.展开更多
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 relaxat...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.展开更多
Owing to the inhomogeneous state resulting from the doping of a small number of Eu ions into Laa/3Sr5/3Mn2O7, from the resulting single crystal （La0.8Eu0.2）a/3Sr5/3Mn2O7 we have observed the magnetization jump, the ...Owing to the inhomogeneous state resulting from the doping of a small number of Eu ions into Laa/3Sr5/3Mn2O7, from the resulting single crystal （La0.8Eu0.2）a/3Sr5/3Mn2O7 we have observed the magnetization jump, the resistivity jump, as well as the relaxation phenomena. For （Lao.sEuo.2）a/3Sr5/3Mn2O7, it has a very delicate ground state due to the interplays among spin, charge, orbital, lattice degrees of freedom. Consequently, the magnetization state is sensitive to temperature, magnetic field, as well as time. Meanwhile, the evolution of the magnetization with time shows a spontaneous jump when both the temperature and the magnetic field are constant. Similar step-like behaviours are also observed in resistivity. All these results suggest that Eu doping can greatly modulate the physical properties of Laa/3Sr5/3Mn2O7 and cause such interesting behaviours.展开更多
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-anthracenecarb...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.展开更多
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...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.展开更多
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. ...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.展开更多
When a ferromagnet(FM)couples to a spin glass(SG),the hidden nature of SG may imprint on the FM via their interfacial coupling,probably resulting in elongated magnetic relaxation and enhanced unidirectional and uniaxi...When a ferromagnet(FM)couples to a spin glass(SG),the hidden nature of SG may imprint on the FM via their interfacial coupling,probably resulting in elongated magnetic relaxation and enhanced unidirectional and uniaxial anisotropies.In parallel with the study of interfacial roles,e.g.interfacial coupling and matching,we focused on the influence of the competing interactions in SG(JSG)on the magnetic relaxation properties of SG/FM bilayer and the FM magnetization reversal involving exchange bias field(HE)and coercivity(HC).A fastest decay of relaxation in SG/FM bilayer is found at an intermediate JSG^5.2 erg/cm2 and the relaxation parameters related to JSG are nonmonotonic.On the other hand,a pronounced HE of^0.26 kOe is observed at small JSG,and as JSG increases larger than 2.275 erg/cm2,HE decreases by an order of magnitude and levels off,i.e.,a net EB remains.He is sensitive to JSG only at JSG above 2.275 erg/cm2 and exhibits a minimum value at JSG=4.55 erg/cm2,just below 5.2 erg/cm2 where the relaxation decay is the fastest.Microscopic analysis unravels that the net magnetization associated with unidirectional magnetic stabilization and the large-area FM-like domains in SG are favored at small JSG,while with increasing JSG,the SG spins spontaneously reverse and thus the energy barriers are smeared out.A high susceptibility and a strong interfacial coupling lead to FM magnetization reversal under weaker fields and thus a decrease in coercivity.For too large JSG(exceeding 5.2 erg/cm2),magnetic frustration extends over the domains in SG meanwhile fierce energy competition occurs frequently,resembling enhanced quantum fluctuations.As a result,dynamic relaxation and statistic coercivity are both recovered.This work tells us that the independent modulations of unidirectional and uniaxial anisotropies are possible in SG-based systems through precisely controlling JSG,which is desired for application in the read/write head in future data storage media.展开更多
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 rat...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.展开更多
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 t...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.展开更多
Due to the ionic feature of the lanthanide ions,to straightly bridge two lanthanide(Ln)ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnet...Due to the ionic feature of the lanthanide ions,to straightly bridge two lanthanide(Ln)ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization(QTM)for single-molecule magnets(SMMs),a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent.Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ)complexes-{[LnL_(A)(4-NH_(2)py)_(5)]_(2)(μ-Cl)}[BPh_(4)]_(3)(For L_(A)^(-)=1-AdO^(-),1Ln;for L_(A)^(-)=~tBuO^(-),2Ln;Ln=Dy,Gd).More uniquely,the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ)ions with local C_(5v)symmetry.The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K(τ_(2K)=2706.89 and 1437.05 s for 1Dy and 2Dy)compared to the diluted ones with the approaching magnetic property of the C_(5v)motifs(τ_(2K)=0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y).Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic,it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.展开更多
基金Project supported by the Nature Science Foundation of Shaanxi Province (2023-JC-YB-137)National Natural Science Foundation of China (21901200)。
文摘Structural fine-tuning is of significant importance to enhance the magnetic anisotropy and elucidate the magneto-structural relationship for single molecule magnets(SMMs).For this purpose,two mononuclear Dy^(3+) SMMs:[Dy{HB(pz)3}2(Sal)](1) and [Dy{HB(pz)_(3)}_(2)(MeO-Sal)](2),where HB(pz)_(3)^(-)represents hydro tris(pyrazolyl)borate,Sal denotes salicyiaidehyde and MeO-Sal stands for 5-methoxysalicylaldehyde,were designed and synthesized.Single crystal X-ray diffraction tests show that the two SMMs have very similar eight-coordinated molecule structures,although the introducing of-MeO substituent on salicyiaidehyde ligand induces the changes on the molecule packing mode and the space group.Both the two SMMs have a Dy-O_(aryloxidebond) that is significantly shorter than other Dy-O/N bonds,which defines the orientation of main anisotropy axis of the ground Kramers doublets and engenders the slow relaxation of the magnetization behavior,as evidenced by the magnetic susceptibility and the ab initio calculation.Though with an electron-donating substituent on the axial Sal ligand in 2,the collective magnetic anisotropy is not enhanced and the corresponding magneto-structural relationship is discussed based on the experimental and theoretical calculation results.In addition,as neutral molecules,1 and 2 are soluble in several common organic solvents,like CH_(2)Cl_(2),CHCl_(3),THF and so on.
基金supported by the National Natural Science Foundation of China(21571092,21403102)the Natural Science Foundation of Shandong Province(ZR2012BQ023)the University Scientific Research Development Plan of the Education Department of Shandong Province(J14LC10)
文摘Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=Pamoic acid, DMA=dimethylacetamide, DMF=N,N-dimethylformamide）, have been synthesized by the reaction of Ln（NO3）a-6H20 with pamoic acid through layer diffusion method. These complexes were characterized by single crystal X-ray diffraction, infrared spectroscopy （IR）, thermogravimetric analysis （TGA）, fluorescence and magnetic measurements. Solvents and lanthanide atoms in the reaction play an important role in controlling different structures. Type I demonstrated 1-D linear chain structure connected by Ln atoms and PA ligands. Type II exhibited non-interpenetrating 3-D 6-connected 43612 nets based on binuclear [Ln2（CO2）6（DMF）4] cores. Magnetic properties of complexes 1-4 were investigated in details. Complex 1 shows significant magnetocaloric effect with -△Sm=20.37 J kg^-1 K^-1 at 3.0 K and 7 T. Complex 2 exhibits slow relaxation of the magnetization. Complexes 3-6 exhibit both ligand- and metal-centered fluorescent properties. Complex 6 demonstrates fluorescent sensing of DMF and Cu^2＋ ion.
基金the National KeyR&D Program of china Nos 201YFA03032032018YFA0306004)the National Natural Science Foundation of China(No.21731003).
文摘Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2·15H_(2)O(3)and{Co(H_(2)O)2[Ir(ppyCOO)_(2)(bpy)]_(2)}·2CH_(3)OH·3H_(2)O(4),have been synthe-sized by combining paramagnetic Co^(Ⅱ)ion with luminescent Ir^(Ⅲ)-metalloligand,[Ir(ppyCOOH)_(2)(bpy)][Ir(ppyCOO)_(2)(bpy)]·5H_(2)O(1),where ppyCOOH=3-(pyridin-2-yl)benzoic acid and bpy=2,2'-bipyridyl.Owing to the variable charged states of compound 1 at dif-ferent pH,compounds 2 and 3 are discrete ionic complexes containing hydrated Co^(2+)cations and deprotonated[Ir(ppyCOO)_(2)(bpy)]-anions as well as coexisting neutral[Ir(ppyCOO)(ppyCOOH)(bpy)](for 2)or Co(H_(2)O)_(4)[Ir(ppyCOO)_(2)(bpy)]_(2) trinuclear molecule(for 3).Whereas compound 4 consists of self-assembled two-dimensional coordination polymer with Co-metalloligand dative bonds.The hexa-coordinated Co^(Ⅱ)cores in all complexes display octahedral geometries with varying degrees of distortion.In a bias dc field,the ac susceptibilities for 2-4 reveal slow magnetic relaxation.Moreover,the solid-state phosphorescence is observed for compounds 2 and 3 due to weak supramolecular interaction between Co^(Ⅱ)ion and Ir-moiety but is severely quenched for 4,where the Co center is strongly connected to the metalloligand.To the best of our knowledge,this is the first report of Ir-Co systems showing both slow magnetization relaxation and photoluminescence.
基金Supported by the National Natural Science Foun-dation of Chine(10174056)
文摘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 andΔT 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.
基金supported by the National Key Research and Development Program of China(No.2021YFA1600304)Joint Fund for Regional Innovation and Development(No.U20A2073)+4 种基金National Natural Science Foundation of China(Nos.22373048,21973038,61904119 and 22105089)Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry(No.20212BCD42018)US National Science Foundation(NSF,No.CHE-2055499)the Interdisciplinary program of Wuhan National High Magnetic Field Center(No.WHMFC202133)the support of the NSF Research Traineeship Program(No.DGE-2152168)。
文摘Two CoⅡ-based complexes,{[Co(dps)_(2)(N_(3))_(2)]·H_(2)O}_n(1)and[Co(dps)_(2)(N_(3))_(2)]_n(2),show a 1D chain and a 3D network,respectively.The central CoⅡions in the complexes have the same coordination environment with the[Co(dps)_(4)(N_(3))_(2)]unit.Although the differences in crystal parameters are nearly negligible,their magnetic properties are very different.AC susceptibility data show that 1 behaves as a typical field-induced single-ion magnet(SIM)with the out-of-phase(χ_(M)”)signals,while 2 shows ac signals ofχ_(M)”without peaks even under applied dc filed within our measurement window.Far-IR magneto-spectra(FIRMS)show strong spin-phonon couplings at 0 T in 2,likely making the magnetic relaxation in 2 fast,while the couplings are negligible in 1.Small spin-phonon coupling in 1 likely leads to slower magnetic relaxation,making 1 a SIM.The difference in the properties is due to the structural rigidity of 2 in its 3D network,leading to stronger spin-phonon coupling.Combined high-field EPR(HF-EPR)and FIRMS studies give spin-Hamiltonian parameters,including D=64.0(9)cm^(-1),|E|=15.7(2)cm^(-1)for 1 and D=80.0(2)cm^(-1),|E|=19.0(1)cm^(-1)for 2.
基金National Natural Science Foundation of China(Grant Nos.11674187 and 51871127)Technology on Electronic Test&Measurement Laboratory(Grant No.6142001180103).
文摘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.
基金Project supported by the National Natural Science Foundation of China （Grant No 10505029）.
文摘The quantum tunnelling of magnetization （QTM） in single crystals of the single molecule magnet （Mn1-xCrx）12- Ac （x=0, 0.03, 0.04, 0.05） has been investigated. In comparison with its parent Mnl2-Ac, a greater rate of magnetization relaxation and a lower effective potential-energy barrier have been observed in Cr-doping samples. This modulation of QTM due to the Cr-doping could be attributed to the small change of Sz due to the smaller spin of Cr itself and additional intrinsic but distributed transverse and longitudinal anisotropy raised by a subtle change of the local environment in the magnetic Mn12 core.
基金Project supported by the National Natural Science Foundation of China(91963123)the State Key Laboratory of Solidification Processing in NWPU(SKLSP202020)+1 种基金the Ten Thousand Talents Plan of Zhejiang Province of China(2018R52003)the Fundamental Research Funds for the Provincial University of Zhejiang(GK199900299012-022)。
文摘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.
基金Project supported by the National Natural Science Foundation of China (21372112,21701039)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (201802099)。
文摘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.
基金Project supported by the National Natural Science Foundation of China(21901152)Natural Science Foundation of Henan Province(222300420509)。
文摘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.
基金financially supported by the 973 Program of China(Nos.2012CB821700 and 2014CB845600)the NNSF of China(Nos.21031002 and 21290171)MOE Innovation Team (No.IRT13022) of China
文摘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.
基金Project supported by the National Natural Science Foundation of China (21901200)the Natural Science Foundation of Shaanxi Province(2019JQ-489,2019JZ-44)+3 种基金the Scientific Research Program of Shaanxi Provincial Education Department (18JK0607)the Young Talent Fund of Xi’an Association for Science and Technology (095920201319)the 111 project (B12015)the Postgraduate Innovation and Practice Training Program of Xi’an Shiyou University(YCS202121001)。
文摘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.
基金supported by the National Natural Science Foundation of China (Grant No 50672126)the Inner Mongolia Natural Science Foundation,China (Grant No 200607010102)
文摘Owing to the inhomogeneous state resulting from the doping of a small number of Eu ions into Laa/3Sr5/3Mn2O7, from the resulting single crystal （La0.8Eu0.2）a/3Sr5/3Mn2O7 we have observed the magnetization jump, the resistivity jump, as well as the relaxation phenomena. For （Lao.sEuo.2）a/3Sr5/3Mn2O7, it has a very delicate ground state due to the interplays among spin, charge, orbital, lattice degrees of freedom. Consequently, the magnetization state is sensitive to temperature, magnetic field, as well as time. Meanwhile, the evolution of the magnetization with time shows a spontaneous jump when both the temperature and the magnetic field are constant. Similar step-like behaviours are also observed in resistivity. All these results suggest that Eu doping can greatly modulate the physical properties of Laa/3Sr5/3Mn2O7 and cause such interesting behaviours.
基金Project supported by the National Natural Science Foundation of China(21671029)Innovation andEntrepreneurship Team of Inorganic Optoelectronic Functional Materials for Chongqing Yingcai(cstc2021ycjh-bgzxm0131)+3 种基金MajorProject of the Science and Technology Research Program of Chongqing Education Commission of China(KJZD-M202100501)theInnovation Program for Chongqing’s Overseas Returnees(cx2019037)Natural Science Foundation of Chongqing,China(cstc2021jcyj-msxmX0380)Chongqing Normal University(21XLB034)。
文摘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.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22222103,22173015,22025101,21801037,91961114 and 21871039)the Fundamental Research Funds for Central University,China。
文摘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.
基金supported by the NSF of China(Nos.21031002,21421001)Natural Science Fund of Tianjin,China(No.15JCZDJC38800)
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.11774045)the Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science(No.20180510008)the Fundamental Research Funds for Central Universities(Nos.N182410008-1 and N180506001)。
文摘When a ferromagnet(FM)couples to a spin glass(SG),the hidden nature of SG may imprint on the FM via their interfacial coupling,probably resulting in elongated magnetic relaxation and enhanced unidirectional and uniaxial anisotropies.In parallel with the study of interfacial roles,e.g.interfacial coupling and matching,we focused on the influence of the competing interactions in SG(JSG)on the magnetic relaxation properties of SG/FM bilayer and the FM magnetization reversal involving exchange bias field(HE)and coercivity(HC).A fastest decay of relaxation in SG/FM bilayer is found at an intermediate JSG^5.2 erg/cm2 and the relaxation parameters related to JSG are nonmonotonic.On the other hand,a pronounced HE of^0.26 kOe is observed at small JSG,and as JSG increases larger than 2.275 erg/cm2,HE decreases by an order of magnitude and levels off,i.e.,a net EB remains.He is sensitive to JSG only at JSG above 2.275 erg/cm2 and exhibits a minimum value at JSG=4.55 erg/cm2,just below 5.2 erg/cm2 where the relaxation decay is the fastest.Microscopic analysis unravels that the net magnetization associated with unidirectional magnetic stabilization and the large-area FM-like domains in SG are favored at small JSG,while with increasing JSG,the SG spins spontaneously reverse and thus the energy barriers are smeared out.A high susceptibility and a strong interfacial coupling lead to FM magnetization reversal under weaker fields and thus a decrease in coercivity.For too large JSG(exceeding 5.2 erg/cm2),magnetic frustration extends over the domains in SG meanwhile fierce energy competition occurs frequently,resembling enhanced quantum fluctuations.As a result,dynamic relaxation and statistic coercivity are both recovered.This work tells us that the independent modulations of unidirectional and uniaxial anisotropies are possible in SG-based systems through precisely controlling JSG,which is desired for application in the read/write head in future data storage media.
文摘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.
基金Project supported by the National Key Research and Development Program of China(Grant No.2021YFA1400303)the National Natural Science Foundation of China(Grant No.12227806)。
文摘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.
基金supported by the National Natural Science Foundation of China(No.22375157)the State Key Laboratory of Electrical Insulation and Power Equipment(No.EIPE23405)+2 种基金the Fundamental Research Funds for Central Universities(No.xtr052023002)the Special Support Plan of Shaanxi Province for Young Top-notch Talentthe Medical-Engineering Cross Project of the First Affiliated Hospital of XJTU(No.QYJC02)。
文摘Due to the ionic feature of the lanthanide ions,to straightly bridge two lanthanide(Ln)ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization(QTM)for single-molecule magnets(SMMs),a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent.Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ)complexes-{[LnL_(A)(4-NH_(2)py)_(5)]_(2)(μ-Cl)}[BPh_(4)]_(3)(For L_(A)^(-)=1-AdO^(-),1Ln;for L_(A)^(-)=~tBuO^(-),2Ln;Ln=Dy,Gd).More uniquely,the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ)ions with local C_(5v)symmetry.The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K(τ_(2K)=2706.89 and 1437.05 s for 1Dy and 2Dy)compared to the diluted ones with the approaching magnetic property of the C_(5v)motifs(τ_(2K)=0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y).Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic,it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
