Structural phase transition and magnetic properties of layered organic-inorganic hybrid compounds: p-Haloanilinium tetrachlorocuparate(II)

Compounds of the general formula A₂CuCl₄, (where A = 4-fluoroanilinium (1) and 4-chloroanilinium (2)) were prepared, structurally characterized and their thermal and magnetic properties studied. These compounds have a layered structure, distorted perovskite, where layers of CuCl₄²⁻ are sandwiched between a 4-haloanilinium cation bilayer. A single crystal X-ray diffraction study on (4-fluoroanilinium)₂CuCl₄, (1), shows that it crystallizes in the monoclinic P2₁/c space group with cell dimensions a = 15.5113(5) Å, b = 7.3788(2) Å, c = 7.0929(2) Å, β = 99.004(2)°, volume 801.81(4) Å³ at 150 K. Compound 2, (4-chloroanilinium)₂CuCl₄, crystallizes isostructurally to 1 at RT, but at 150 K it adopts the Pccn space group. This structural transition for 2 is reversible, and has been observed using Differential Scanning Calorimetric (DSC) measurements. The dc-magnetic studies using a SQUID magnetometer suggest that both compounds are soft ferromagnets and show an onset of long range magnetic ordering below 9 K. The ac-susceptibility measurements confirm the presence of this ferromagnetic ordering in both the compounds.     

Frontiers in frustrated magnetism

This article discusses at a qualitative level a number of issues at the forefront of current understanding and developments in frustrated quantum magnetism. The focal point of the presentation is the spin liquid, which is introduced in terms of (un)broken spin and lattice symmetries. An overview of the full spectrum of research activity in the field is obtained by considering selected examples from experimental approaches to realising spin-liquid states, from theoretical efforts which seek both to classify spin liquids according to their physical properties and to broaden the search for spin-liquid behaviour, and from numerical techniques which offer the prospect of qualitatively new insight into frustrated spin systems.     

Magnetic molecular wheels and grids - the need for novel concepts in “zero-dimensional” magnetism

Supramolecular chemistry has allowed the production, by self-assembly, of inorganic complexes with a [N × N] square matrix-like configuration of N² metal centers. Interest in these systems is driven by the potential applications in information technology suggested by such a “two-dimensional” (2D), addressable arrangement of metal ions. From the magnetic perspective [N × N] grids constitute molecular model systems for magnets with extended interactions on a square lattice, which have gained enormous attention in the context of high-temperature superconductors. Numerous [2 × 2] grids as well as a few [3 × 3] grids with magnetic metal ions such as Cu(II), Ni(II), Co(II), Fe(II), and Mn(II) have been created. Magnetic studies unraveled a remarkable variety in their magnetic properties, which will be reviewed in this work with emphasis on the underlying physical concepts. An intriguing issue is the connection of [2 × 2] and [3 × 3] grids with “one-dimensional” (1D) rings, as experimentally realized in the molecular wheels. For a [2 × 2] square of spin centers the distinction between a 2D grid and a 1D ring is semantic, but also a [3 × 3] grid retains 1D character: it is best viewed as an octanuclear ring with an additional ion “doped” into its center. Challenging familiar concepts from conventional magnets, the current picture of elementary excitations in antiferromagnetic rings will be discussed, as a prerequisite to understand the complex [3 × 3] grids.     

Magnetic Properties of Iron Clusters in Silver

Time differential perturbed γ-γ angular correlation technique was used to measure the magnetic hyperfine field (MHF) at Tb sites in the intermetallic compound Tb₃In₅ using the ¹⁴⁰La → ¹⁴⁰Ce nuclear probe. The measurements were carried out in the temperature range of 8 to 295 K. Two different temperature dependent magnetic frequencies were observed below 30 K, which were assigned as ¹⁴⁰Ce substituting the two inequivalent Tb sites in the orthorhombic structure of Tb₃In₅. The temperature dependence of MHF also shows a possible deviation from an expected Brillouin-like behavior for temperatures below 18 K. A Néel transition at 27 K was observed from magnetization measurements in the samples. The magnetization as a function of the applied magnetic field was measured at two temperatures, 5 and 40 K, and the results show antiferromagnetic and a typical paramagnetic behavior, respectively. In both cases it was not observed saturation under high magnetic field.     

Metal (Fe, Co, Ni) Nanoparticles in Silica Gels: Preparation and Magnetic Properties

Metal containing silica gels with a Me/Si molar ratio between 0.01 and 0.2 are submitted to thermal treatment under hydrogen within the temperature range 600 to 1000°C. The changes occurring during these treatments are followed by X-ray diffraction, transmission electron microscopy, Mössbauer spectrometry and static magnetization measurements.During these treatments, nickel is nearly totally reduced to metal particles, the mean size of which increases from 3 to 10 nm with increasing temperature, but does not vary appreciably with nickel content. These particles exhibit a classical superparamagnetic behavior and are stable towards reoxidation when reexposed to air at room temperature.Iron and cobalt behave in a notably different manner. First, in both cases, silicates may be formed during the thermal treatment and consequently the reduction to the metallic state is not complete unless it occurs at high temperature (1000°C and above). Secondly, the particles formed are much less stable toward reoxidation, especially in the case of iron. Accordingly, the evolution of the magnetic behavior is much more complex than in the case of nickel.     

MAl_(12)(M=Ni、Mn)及其阴离子团簇的几何结构和磁性的计算研究

采用密度泛函理论(density functional theory,DFT)中的广义梯度近似(generalized gradient approximation,GGA)分别对Al_(13)和MAl_(12)(M=Ni、Mn)四种初始结构的中性和一价阴离子团簇进行计算研究.发现中性和阴离子团簇的基态几何结构均保持I_h对称性,并且基态阴离子团簇还具有较高的运动学稳定性.电磁性质计算显示:基态的中性和阴离子NiAl_(12)团簇分别带有2_(μB)、3_(μB)的磁矩,Ni原子的磁性几乎完全淬灭;而MnAl_(12)团簇分别带有7_(μB)、6_(μB)的磁矩,Mn原子的磁矩主要由3d轨道提供.基态团簇的表面原子出现了自旋分裂,与中心原子呈现出铁磁性作用.对垂直电离能和垂直亲和能的分析表明:中心原子被替代之后,团簇的得电子能力和失电子能力都有所降低.     

A theoretical STM study of Co n /Pt(111)

It is shown that by ‘stacking’ together a semi-infinite sample subsystem with a semi-infinite tip subsystem, difficulties with respect to a common Fermi level for the whole system can approximately be overcome in all those cases when the substrate (serving as lead) and the second lead are different materials. Based on this procedure by means of the spin-polarized (fully) relativistic screened Korringa–Kohn–Rostocker method and an equivalent Kubo equation, theoretical spin-polarized STM spectra for Pt(111)/Co _n /Cr₁₅ W₂₂/Cu(111) with respect to an applied external magnetic field are evaluated in terms of difference conductivities as a function of the corresponding free energy. These spectra are interpreted using layer-resolved contributions to the difference conductivities in order to indicate which parts of the sample dominate changes in the tunneling current caused by changing the orientation of the magnetization. Also shown are estimates of the time-scales to switch from perpendicular to in-plane and vice versa. All investigated properties suggest that different situations apply when the number of Co layers on top of Pt(111) is increased from one to three.     

双功能镧系化合物:合成、结构、磁性和荧光性质

利用N-succinopyridine（HL）配体,成功合成了2个同构型镧系化合物[Ln（HL）₂（H₂O）₄]Cl₃（Ln=Pr（1）,Eu（2））并对其进行了结构表征。1和2均由羧酸配体双桥联金属离子形成1D链结构,再通过氢键进一步相互连接构成了3D超分子结构。变温磁化率测试表明1中Pr（Ⅲ）离子之间存在反铁磁相互作用,而在2中,Eu（Ⅲ）离子之间则表现出弱铁磁相互作用。固态发光测试观察到2可以发出很强的红光,但由于Pr（Ⅲ）离子的能隙较大,未观察到1的特征峰。