A linear Cu-Gd-Cu-Gd complex derived from the assembly reaction of [NaCuH3L] and [Gd(thd)3(H2O)2] (H3L = meso-1,2-diphenyl-1-(2-oxybenzamido)-2-(2-oxy-3-ethoxybenzylideneamino)ethane and Hthd = 2,2,6,6-tetra-methyl-3,5-heptanedione)

A linear tetranuclear Cu^II-Gd^III-Cu^II-Gd^III complex [Cu^IIL^dpen(meso)Gd^III(thd)₂(H₂O)]₂ was synthesized from the reaction of [NaCu^IIL^dpen(meso)(DMF)] with [Gd^III(thd)₃(H₂O)₂], and the structures and magnetic properties were investigated, where H₃L^dpen(meso) = meso-1,2-diphenyl-1-(2-hydroxybenzamido)-2-(2-hydroxy-3-ethoxybenzylideneamino)ethane and Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione. The Cu^II complex component [NaCu^IIL^dpen(meso)(DMF)] has a one-dimensional (1D) chain structure, in which the Na⁺ ion is coordinated by two phenoxo and an ethoxy oxygen atoms of a Cu^II complex and an amido oxygen atom of the adjacent Cu^II unit to produce the 1D structure, in which the diphenylethylenediamine moieties have the array of {(1R,2S)-Na-(1S,2R)}_1∞. The assembly reaction of the Cu^II and Gd^III components gave a linear complex with the array of Cu(1)-Gd(1)-Cu(2)-Gd(2), in which two diphenylethylenediamine moieties have the same chirality of (1R,2S)-(1R,2S) or (1S,2R)-(1S,2R). Two linear Cu(1)-Gd(1)-Cu(2)-Gd(2) units are linked by hydrogen bonds through two water molecules to give a cyclic structure with a center of symmetry. The temperature dependence of the magnetic susceptibilities and field-dependent magnetization revealed the ferromagnetic interaction between the Cu^II and Gd^III ions within the linear chain.     

Characterization of two linear chain compounds: Ferromagnet NiCl2(CH3OH)2(1,4-dioxane)0.5 (1) and paramagnet [NiCl2(H2O)2(1,4-dioxane)](1,4-dioxane) (2)

The solvent-mediated crystal-to-crystal transformation was observed from yellow crystal of NiCl₂(CH₃OH)₂(1,4-dioxane)_0.5 (1) to green crystal of [NiCl₂(H₂O)₂(1,4-dioxane)](1,4-dioxane) (2) under high humidity or adding of H₂O in CH₃OH/1,4-dioxane solution. The μ-Cl₂ bridge in 1 replaced by 1,4-dioxane bridge in 2. In 1, the chlorine-bridged linear chains of NiCl₂(CH₃OH)₂ and 1,4-dioxane molecules stack along the b- and c-axis alternatively with hydrogen bonds intrachain, interchain, between chain and solvent. These hydrogen bonds and dipolar interaction between ferromagnetic coupling chlorine-bridged chains result in long-range ferromagnetic ordering at 3.1 K and a strong frequency dependence of the ac-susceptibilities associated to domain structures with very large shape anisotropy was observed below 3.1 K. In 2, layers of 1,4-dioxane-bridged linear chains of NiCl₂(H₂O)₂(1,4-dioxane) are intercalated by layer of 1,4-dioxane molecules with hydrogen bonds between chain and solvent. Compound 2 is paramagnet to 2 K.     

A new series of lanthanoid containing Keggin-type germanotungstates with acetate chelators: [{Ln(CH3COO)GeW11O39(H2O)}2] {Ln=Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb}

A series of head-on complexes of lanthanoid containing germanotungstates was isolated from a one pot reaction in an acetate buffer at pH 4.5. This convenient approach brought forward the [{Ln(CH₃COO)GeW₁₁O₃₉(H₂O)}₂]¹²⁻ (Ln=Eu^III, Gd^III, Tb^III, Dy^III, Ho^III, Er^III, Tm^III, and Yb^III) family with acetate chelators in the rarely observed μ₂: η²-η¹ mode. All compounds were structurally characterized using various solid state analytics, such as single crystal X-ray diffraction, FT-IR spectroscopy, and thermogravimetric analysis. The isostructural polyanions crystallize in the monoclinic system (S.G. P2₁/c). Temperature-dependent magnetic susceptibility measurements were performed on the Gd^III-complex which exhibits near perfect Curie-type behavior.     

Local ordering and magnetism in Ga0.9Fe3.1N

Prior investigations of the ternary nitride series Ga_1-xFe_3+xN (0≤x≤1) have indicated a transition from ferromagnetic γ′-Fe₄N to antiferromagnetic “GaFe₃N”. The ternary nitride “GaFe₃N” has been magnetically and spectroscopically reinvestigated in order to explore the weakening of the ferromagnetic interactions through the gradual incorporation of gallium into γ′-Fe₄N. A hysteretic loop at RT reveals the presence of a minority phase of only 0.1-0.2 at%, in accord with the sound two-step synthesis. The composition of the gallium-richest phase “GaFe₃N” was clarified by Prompt Gamma-ray Activation Analysis and leads to the berthollide formula Ga_0.91(1)Fe_3.09(10)N_1.05(7). Magnetic measurements indicate a transition around 8 K, further supported by Mössbauer spectral data. The weakening of the ferromagnetic coupling through an increasing gallium concentration is explained by a simple Stoner argument. In Ga_0.9Fe_3.1N, the presence of iron on the gallium site affects the magnetism by the formation of 13-atom iron clusters.     

多价态钼多酸配合物[Mo(Ⅳ)Mo2(Ⅴ)O7(Phen)]的晶体结构及性质

用水热法合成了一种新的多价钼多酸配合物[Mo(Ⅳ)Mo2(Ⅴ)O7(Phen)],并用X射线衍射、元素分析、红外光谱、热重-差热、荧光光谱和磁化率等对其进行了表征.X射线衍射分析表明,配合物晶体属于单斜晶系,P2(1)/c空间群,由十二员环和八员环构成二维网状结构.配合物中强π-π堆积作用构筑成层状三维超分子,稳定了配...     

Magnetism and electronic structure of Mn- and V-doped zinc blende ZnTe from first-principles calculations

By means of the first-principles full potential linearized augmented plane-wave method within the local density approximation for the exchange-correlation functional, we have investigated the magnetism and electronic structure of Mn- and V-doped zinc blende ZnTe. Total energy calculations show that, for high doping concentration (12.5%), ZnTe:Mn has an antiferromagnetic ground state while the ferromagnetic state is more favorable than the antiferromagnetic state for ZnTe:V. Furthermore, ZnTe with a low doping of Mn (6.25%) has a stable ferromagnetic ground state, which is in agreement with the experimental results. The calculated magnetic moment of ZnTe doped with Mn (V) mainly originates from transition metal Mn (V) atom with a little contribution from Te atom due to the hybridization between Mn (V) 3d and Te 5p electrons. Electronic structure indicates that Mn-doped ZnTe is a semiconductor, but V-doped ZnTe shows a half-metallic characteristic. We also discuss the difference between electronic and magnetic properties for ZnTe doped with 12.5% and 6.25% Mn.     

Interplay of Sm and Co spins in SmCoAsO

We present detailed magnetization and magneto-transport studies on the title compound SmCoAsO. In a recent paper we reported (Awana et al., 2010 [1]) the complex magnetism of this compound. SmCoAsO undergoes successive paramagnetic (PM)-ferro-magnetic (FM)-anti-ferro-magnetic (AFM) transitions with decrease in temperature. This is mainly driven via the c-direction interaction of Sm^4f (SmO layer) spins with adjacent (CoAs layer) ordered Co^3d spins. In this article we present an evidence of kinetic arrest for FM-AFM transition. The isothermal magnetization (MH) loops for SmCoAsO exhibited the meta-magnetic transitions at 6, 8 and 10 K at around 80, 60 and 50 kOe fields, respectively, with characteristic hysteresis shoulders along with the non-zero moment at the origin, thus suggesting the possibility of kinetic arrest. Suggested kinetic arrest is further evident in zero field-cooled (ZFC) and field-cooled (FC) hysteresis under high fields of up to 140 kOe magnetization (MT) and the magneto-transport measurements R(T)H during FM-AFM transition. The time dependent moment experiments exhibited very small (∼2-3%) increase of the same below 20 kOe and decrease for 30 kOe at 15 K.     

Study of ferromagnetism in Bi2S3 and ZnS nanocrystalline powders

Results of magnetic measurements suggested that Bi₂S₃ and ZnS nanocrystalline powders prepared by hydrothermal method could possibly exhibit room temperature ferromagnetism. The measured saturation magnetization of the powders increases with an increase of annealing temperature from 300 to 500 °C. Ab initio calculations suggested that the cation vacancies on the surface of Bi₂S₃ and ZnS nanograins could be responsible for the observed magnetic moments. Heat-treatment of Bi₂S₃ or ZnS nanocrystalline powders in Bi or Zn vapor could bring about an enhancement of ferromagnetism. The calculation results indicated that the interstitial Bi or Zn atoms in Bi₂S₃ (0 0 1) or ZnS (0 0 1) surface could induce magnetic moments.     

Electrical and magnetic characterization of a molecular material {[Ru(bpy)3][Fe(dca)3]2}n

Electrical and magnetic properties of {[Ru(bpy)₃][Fe(dca)₃]₂}_n (bpy=2,2′-bipyridine, dca=dicyanamide) have been studied. The compound is a non-extrinsic type of semiconductor and paramagnetic in nature. Mössbauer spectroscopy has established the presence of high spin Fe(II) as one major species in this compound, and no high spin-low spin transition of Fe(II) was detected down to 80 K under dark. The photo-response of electrical conductivity with time shows interesting behavior with repeated exposure.     

A first-principles study of ferromagnetism in Pd-doped ZnO

The electronic structures and magnetic properties of Pd-doped ZnO have been studied by the full-potential linear augmented plane wave (FLAPW) method using the generalized gradient approximation (GGA). We find that Pd-doped ZnO becomes 100% spin polarized when Pd substitutes for Zn in the 2×2×2 ZnO supercell. The supercell magnetic moment reaches 2.0μ_B. Long-range ferromagnetic (FM) coupling is obtained with all Pd dopant configurations, and a Curie temperature as high as 860 K is predicted for the ground-state configuration. The hybridized Pd(4d)-O(2p)-Zn(4d)-O(2p)-Pd(4d) chain formed through p-d-like coupling is responsible for the long-range room-temperature FM coupling. We discuss the effect of O vacancies or Zn vacancies on the magnetism as well.