Your browser doesn't support javascript.
Mostrar: 20 | 50 | 100
Resultados 1 - 16 de 16
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Artigo em Inglês | MEDLINE | ID: mdl-32289761

RESUMO

The compound La2-2xSr1+2xMn2O7, x = 0.30 - 0.40, consists of bilayers of ferromagnetic metallic MnO2 sheets that are separated by insulating layers. The materials show colossal magnetoresistance - a reduction in resistivity of up to two orders of magnitude in a field of 7 T - at their three-dimensional ordering temperatures, TC = 90 K - 126 K, and are the layered analogues of the widely studied pseudo-cubic perovskite manganites, R1 xAxMnO3 (R = rare earth, A = Ca, Sr, Ba, Pb). Two distinct short-range orderings - antiferromagnetic fluctuations and correlated polarons, which are related to the magnetic and the lattice degrees of freedom respectively - have previously been discovered in La2 2xSr1+2xMn2O7, x = 0.40, and have each been qualitatively connected to the resistivity. Here, in a comprehensive study as a function of both temperature and magnetic field for the different hole-concentrations per Mn site of x = 0.30 and 0.35, we show that antiferromagnetic fluctuations also appear at temperatures just above TC, and that the intensities of both the antiferromagnetic fluctuations and polaron correlations closely track the resistivity. In particular, for x = 0.35 we show that there is a simple scaling relation between the intensities of the antiferromagnetic fluctuations and the in-plane resistivity that applies for the temperatures and magnetic fields used in the experiments. The results show that antiferromagnetic fluctuations are a common feature of La2 2xSr1+2xMn2O7 with ferromagnetic bilayers, and that there is a close connection between the antiferromagnetic fluctuations and polarons in these materials.

2.
J Phys Chem Lett ; 10(7): 1511-1515, 2019 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-30883126

RESUMO

Spin-crossover nanomaterials have been actively studied in the past decade for their potential technological applications in sensing, actuating, and information processing devices. Unfortunately, an increasing number of the metallic centers become inactive at reduced sizes, presumably due to surface effects, limiting their switching ability and thus the scope of applications. Here we report on the investigation of "frozen" metallic centers in nanoparticles (2-80 nm size) of the spin-crossover compound Fe(pyrazine)[Ni(CN)4]. Magnetic measurements reveal both high-spin and low-spin residual fractions at atmospheric pressure. A pressure-induced transition of the high-spin residue is observed at around 1.5 GPa by synchrotron Mössbauer spectroscopy. We show that it is equivalent to a downshift of the transition temperature by ca. 400 K due to the size reduction. Unexpectedly, small-angle neutron scattering experiments demonstrate that these high-spin residual centers are not confined to the surface, which contradicts general theoretical considerations.

3.
Sci Adv ; 4(9): eaat7323, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-30255145

RESUMO

The lack of inversion symmetry in the crystal lattice of magnetic materials gives rise to complex noncollinear spin orders through interactions of a relativistic nature, resulting in interesting physical phenomena, such as emergent electromagnetism. Studies of cubic chiral magnets revealed a universal magnetic phase diagram composed of helical spiral, conical spiral, and skyrmion crystal phases. We report a remarkable deviation from this universal behavior. By combining neutron diffraction with magnetization measurements, we observe a new multidomain state in Cu2OSeO3. Just below the upper critical field at which the conical spiral state disappears, the spiral wave vector rotates away from the magnetic field direction. This transition gives rise to large magnetic fluctuations. We clarify the physical origin of the new state and discuss its multiferroic properties.

4.
Angew Chem Int Ed Engl ; 55(12): 3963-7, 2016 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-26890339

RESUMO

We have determined by polarized neutron diffraction (PND) the low-temperature molecular magnetic susceptibility tensor of the anisotropic low-spin complex PPh4 [Fe(III) (Tp)(CN)3]⋅H2O. We found the existence of a pronounced molecular easy magnetization axis, almost parallel to the C3 pseudo-axis of the molecule, which also corresponds to a trigonal elongation direction of the octahedral coordination sphere of the Fe(III) ion. The PND results are coherent with electron paramagnetic resonance (EPR) spectroscopy, magnetometry, and ab initio investigations. Through this particular example, we demonstrate the capabilities of PND to provide a unique, direct, and straightforward picture of the magnetic anisotropy and susceptibility tensors, offering a clear-cut way to establish magneto-structural correlations in paramagnetic molecular complexes.

5.
Chemistry ; 22(2): 724-35, 2016 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-26728231

RESUMO

Polarized neutron diffraction (PND) experiments were carried out at low temperature to characterize with high precision the local magnetic anisotropy in two paramagnetic high-spin cobalt(II) complexes, namely [Co(II) (dmf)6 ](BPh4 )2 (1) and [Co(II) 2 (sym-hmp)2 ](BPh4 )2 (2), in which dmf=N,N-dimethylformamide; sym-hmp=2,6-bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate, and BPh4 (-) =tetraphenylborate. This allowed a unique and direct determination of the local magnetic susceptibility tensor on each individual Co(II) site. In compound 1, this approach reveals the correlation between the single-ion easy magnetization direction and a trigonal elongation axis of the Co(II) coordination octahedron. In exchange-coupled dimer 2, the determination of the individual Co(II) magnetic susceptibility tensors provides a clear outlook of how the local magnetic properties on both Co(II) sites deviate from the single-ion behavior because of antiferromagnetic exchange coupling.

6.
Nano Lett ; 14(6): 3481-6, 2014 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-24828234

RESUMO

The implementation of nano-objects in numerous emerging applications often demands their integration in macroscopic devices. Here we present the bottom-up epitaxial solution growth of high-density arrays of vertical 5 nm diameter single-crystalline metallic cobalt nanowires on wafer-scale crystalline metal surfaces. The nanowires form regular hexagonal arrays on unpatterned metallic films. These hybrid heterostructures present an important perpendicular magnetic anisotropy and pave the way to a high density magnetic recording device, with capacities above 10 Terabits/in(2). This method bypasses the need of assembling and orientating free colloidal nanocrystals on surfaces. Its generalization to other materials opens new perspectives toward many applications.

7.
Inorg Chem ; 44(12): 4315-25, 2005 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-15934762

RESUMO

A new family of tetranuclear Ni complexes [Ni(4)(ROH)(4)L(4)] (H(2)L = salicylidene-2-ethanolamine; R = Me (1) or Et (2)) has been synthesized and studied. Complexes 1 and 2 possess a [Ni(4)O(4)] core comprising a distorted cubane arrangement. Magnetic susceptibility and inelastic neutron scattering studies indicate a combination of ferromagnetic and antiferromagnetic pairwise exchange interactions between the four Ni(II) centers, resulting in an S = 4 spin ground state. Magnetization measurements reveal an easy-axis-type magnetic anisotropy with D approximately -0.93 cm(-)(1) for both complexes. Despite the large magnetic anisotropy, no slow relaxation of the magnetization is observed down to 40 mK. To determine the origin of the low-temperature magnetic behavior, the magnetic anisotropy of complex 1 was probed in detail using inelastic neutron scattering and frequency domain magnetic resonance spectroscopy. The spectroscopic studies confirm the easy-axis-type anisotropy and indicate strong transverse interactions. These lead to rapid quantum tunneling of the magnetization, explaining the unexpected absence of slow magnetization relaxation for complex 1.

9.
Inorg Chem ; 44(3): 649-53, 2005 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-15679397

RESUMO

We report inelastic neutron scattering (INS) studies on a series of Mn(12) derivatives, [Mn(12)O(12)(O2CC6F5)16(H2O)4]z, in which the number of unpaired electrons in the cluster is varied. We investigated three oxidation levels: z = 0 for the neutral complex, z = -1 for the one-electron reduced species and z = -2 for the two-electron reduced complex. For z = 0, the ground state is S = 10 as in the prototypical Mn12-acetate. For z = -1, we have S = 19/2, and for z = - 2, an S = 10 ground state is retrieved. INS studies show that the axial zero-field splitting parameter D is strongly suppressed upon successive electron reduction: D = -0.45 cm(-1) (z = 0), D = -0.35 cm(-1) (z = -1), and D approximately -0.26 cm(-1) (z = -2). Each electron reduction step is directly correlated to the conversion of one anisotropic (Jahn-Teller distorted) Mn3+ (S = 2) to one nearly isotropic Mn2+ (S = 5/2).

10.
Dalton Trans ; (17): 2758-66, 2004 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-15514763

RESUMO

The synthesis and structural characterisation of three small nickel(II) cages are reported, all stabilised by pivalate ligands. The magnetic properties of the cages have been studied by a combination of susceptibility measurements and inelastic neutron scattering. For a dinuclear cage, [Ni2(mu-OH2)(O2CCMe3)4(HO2CCMe3)4] 1 the ground state is S=2, with a ferromagnetic exchange interaction between the Ni(II) centres of J=0.32 meV and D(S=2)=-0.09 meV in the ground state. For a tetranuclear heterocubane cage, [Ni4(mu(3)-OMe)4(O2CCMe3)4(MeOH)4] 2, two ferromagnetic exchange interactions are found and an S=4 ground state observed. While the zero-field splitting of this state cannot be determined unambigiously the most likely value is DS=4=-0.035 meV. For a tetranuclear nickel butterfly, [Ni4(mu3-OH)2(O2CCMe3)6(EtOH)6] 3, three exchange interactions are required, two anti-ferromagnetic and one weakly ferromagnetic; the resulting ground state is S=0. The data enable us to estimate the zero-field splitting of single Ni(II) ions involved in the cage as Di=+1.0 meV. Both and are therefore expected to be new single molecule magnets.

11.
Inorg Chem ; 43(16): 5053-68, 2004 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-15285682

RESUMO

Nine members of a new family of polynuclear ferric complexes have been synthesized and characterized. The reaction of Fe(O(2)CMe)(2) with polydentate Schiff base proligands (H(2)L) derived from salicylidene-2-ethanolamine, followed in some cases by reaction with carboxylic acids, has afforded new complexes of general formulas [Fe(2)(pic)(2)(L)(2)] (where pic(-) is the anion of 2-picolinic acid), [Fe(3)(O(2)CMe)(3)(L)(3)], [Fe(4)(OR)(2)(O(2)CMe)(2)(L)(4)], and [Fe(5)O(OH)(O(2)CR)(4)(L)(4)]. The tri-, tetra-, and pentanuclear complexes all possess unusual structures and novel core topologies. Mössbauer spectroscopy confirms the presence of high-spin ferric centers in the tri- and pentanuclear complexes. Variable-temperature magnetic measurements suggest spin ground states of S = 0, 1/2, 0, and 5/2 for the bi-, tri-, tetra-, and pentanuclear complexes, respectively. Fits of the magnetic susceptibility data have provided the magnitude of the exclusively antiferromagnetic exchange interactions. In addition, an easy-axis-type magnetic anisotropy has been observed for the pentanuclear complexes, with D values of approximately -0.4 cm(-)(1) determined from modeling the low-temperature magnetization data. A low-temperature micro-SQUID study of one of the pentanuclear complexes reveals magnetization hysteresis at nonzero field. This is attributed to an anisotropy-induced energy barrier to magnetization reversal that is of molecular origin. Finally, an inelastic neutron scattering study of one of the trinuclear complexes has revealed that the magnetic behavior arises from two distinct species.

12.
Chemphyschem ; 4(9): 910-26, 2003 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-14562436

RESUMO

We review our recent work in the field of molecular spin clusters and single-molecule magnets, showing how inelastic neutron scattering (INS) can be used to determine magnetic exchange interactions and anisotropy splittings. A general introduction to neutron scattering precedes selected examples, building upon the first determination of exchange coupling in a transition metal complex using INS, through anisotropic exchange in cobalt(II) spin clusters to the determination of exchange interactions in a dodecanuclear nickel(II) wheel. The strength of INS for the accurate determination of anisotropy splittings in single-molecule magnets is revealed. Not only can one determine the axial zero-field splitting parameter D, which plays a key role in single-molecule magnet behavior, but also higher-order terms important in understanding the quantum tunneling behavior. Finally, we review two of our synthetic approaches towards new single-molecule magnets based on nickel, manganese, and iron.

13.
Chemistry ; 8(21): 4867-76, 2002 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-12397588

RESUMO

A cyclic complex [Ni(12)(chp)(12)(O(2)CMe)(12)(thf)(6)(H(2)O)(6)] (1) has been synthesised and studied (chp=6-chloro-2-pyridonate). Complex 1 exhibits ferromagnetic exchange between the S=1 centres, giving an S=12 spin ground state. Detailed studies demonstrate that it is a single-molecule magnet with an energy barrier of approximately 10 K for reorientation of magnetisation. Resonant quantum tunnelling is also observed. The field between resonances allows accurate measurement of D, which is 0.067 K. Inelastic neutron scattering studies have allowed exchange parameters to be derived accurately, which was impossible from susceptibility data alone. Three exchange interactions are required: two ferromagnetic nearest neighbour interactions of approximately 11 and 2 cm(-1) and an anti-ferromagnetic next nearest neighbour interaction of -0.9 cm(-1).

14.
Inorg Chem ; 41(22): 5675-85, 2002 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-12401071

RESUMO

The magnetic exchange interactions in the mixed-valence dodecanuclear polyoxovanadate compounds Na(4)[V(IV)(8)V(V)(4)As(III)(8)O(40)(H(2)O)].23H(2)O, Na(4)[V(IV)(8)V(V)(4)As(III)(8)O(40)(D(2)O)].16.5D(2)O, and (NHEt(3))(4)[V(IV)(8)V(V)(4)As(III)(8)O(40)(H(2)O)].H(2)O were investigated by an inelastic neutron scattering (INS) study using cold neutrons. In addition, the synthesis procedures and the single-crystal X-ray structures of these compounds have been investigated together with the temperature dependence of their magnetic susceptibilities. The magnetic properties below 100 K can be described by simply taking into account an antiferromagnetically exchange coupled tetramer, consisting of four vanadium(IV) ions. Up to four magnetic transitions between the cluster S = 0 ground state and excited states could be observed by INS. The transition energies and the relative INS intensities could be modeled on the basis of the following exchange Hamiltonian: H(ex) = -2J(12)(xy)[S(1x)S(2x)+ S(3x)S(4x)+ S(1y)S(2y)+ S(3y)S(4y)] - 2J(12)(z)[(S(1z)S(2z)+ S(3z)S(4z)] - 2J(23)(xy)[(S(2x)S(3x)+ S(1x)S(4x)+ S(2y)S(3y)+ S(1y)S(4y)] - 2J(23)(z)[(S(2z)S(3z)+ S(1z)S(4z)]. The following sets of parameters were derived: for Na(4)[V(12)As(8)O(40)(H(2)O)].23H(2)O, J(12)(xy)() = J(12)(z)= -0.80 meV, J(23)(xy) = J(23)(z) = -0.72 meV; for Na(4)[V(12)As(8)O(40)(D(2)O)].16.5D(2)O, J(12)(xy) = J(12)(z) = J(23)(xy) = J(23)(z = -0.78 meV; for (NHEt(3))(4)[V(12)As(8)O(40)(H(2)O)].H(2)O, J(12)(xy) = -0.80 meV, J(12)(z) = -0.82 meV, J(23)(xy)() = -0.67 meV, J(23)(z) = -0.69 meV. This study of the same [V(12)As(8)]-type cluster in three different crystal environments allows us to draw some conclusions concerning the applicability on INS in the area of nondeuterated molecular spin clusters. In addition, the effects of using nondeuterated samples and different sample container shapes for INS were evaluated.

15.
Inorg Chem ; 41(16): 4266-74, 2002 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-12160417

RESUMO

The properties of the spin state manifold of the tetranuclear cluster Ni[(OH)(2)Cr(bispictn)](3)]I(5).5H(2)O (bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine) are investigated by combining magnetic susceptibility and magnetization measurements with an inelastic neutron scattering (INS) study on an undeuterated sample of Ni[(OH)(2)Cr(bispictn)](3)]I(5).5H(2)O. The temperature dependence of the magnetic susceptibility indicates an S = (1)/(2) ground state, which requires antiferromagnetic interactions both between Cr(3+) and Ni(2+) ions and among the Cr(3+) ions. INS reveals potential single-ion anisotropies to be negligibly small and enables an accurate determination of the exchange parameters. The best fit to the experimental energy level diagram is obtained by an isotropic spin Hamiltonian H = J(CrNi)(S(1)().S(4)() + S(2)().S(4)() + S(3)().S(4)()) + J(CrCr)(S(1)().S(2)() + S(1)().S(3)() + S(2)().S(3)()) with J(CrNi) = 1.47 cm(-)(1) and J(CrCr) = 1.25 cm(-)(1). With this model, the experimental intensities of the observed INS transitions as well as the temperature dependence of the magnetic data are reproduced. The resulting overall antiferromagnetic exchange is rationalized in terms of orbital exchange pathways and compared to the situation in oxalato-bridged clusters.

16.
Chemistry ; 8(24): 5701-8, 2002 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-12693052

RESUMO

The ground-state properties of a Co3II moiety encapsulated in a polyoxometalate anion were investigated by combining measurements of specific heat, magnetic susceptibility, and low-temperature magnetization with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na12[Co3W(D2O)2(ZnW9O34)2].40D2O (Co3). The ferromagnetic Co3O14 cluster core consists of three octahedrally oxo-coordinated CoII ions. According to the single-ion anisotropy and spin-orbit coupling of the octahedral CoII ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co3 spin cluster is anisotropic and is expressed as H = -2 sigma a = x,y,z (Ja12 S1a S2a + Ja23 S2a S3a), where Ja are the components of the exchange interactions between the CoII ions. To reproduce the INS data, different orientations of the two anisotropic J tensors must be considered, and the following conditions had to be introduced: Jx12 = Jy23, Jy12 = Jx23, Jz12 = Jz23. This result was correlated with the molecular symmetry of the complex. The following set of parameters was obtained: Jx12 = Jy23 = 1.37, Jy12 = Jx23 = 0.218, and Jz12 = Jz23 = 1.24 meV. This set also reproduces in a satisfactory manner the specific heat, susceptibility, and magnetization properties of Co3.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA