Multiferroicity Broken by Commensurate Magnetic Ordering in Terbium Orthomanganite

TbMnO₃ is an important multiferroic material with strong coupling between magnetic and ferroelectric orderings. Incommensurate magnetic ordering is suggested to be vital for this coupling in TbMnO₃, which can be modified by doping at the site of Tb and/or Mn. Our study shows that a self‐doped solid solution Tb_1?xMn_yMnO₃ (y≤x) can be formed with Mn doped into the site of Tb of TbMnO₃. When y is small Tb_1?xMn_yMnO₃ shows both ferroelectric and incommensurate magnetic orders at low temperature, which is similar to TbMnO₃. However, if y is large enough, a commensurate antiferromagnetic ordering appears along with the incommensurate magnetic ordering to prevent the appearance of multiferroicity in Tb_1?xMn_yMnO₃. That is to say, the magnetoeletric coupling can be broken by the co‐existence of a commensurate antiferromagnetic ordering. This finding may be useful to the study of TbMnO₃.     

A novel octanuclear nickel(II)–molybdenum(VI) heterometallic cluster based on the salicylhydroxamate ligand

Salicylhydroxamic acid (H₃shi) is known for its strong coordination ability and multiple coordination modes, and can easily coordinate to metal cations to form compounds with five‐ or six‐membered rings, as well as mono‐, di‐ and multinuclear compounds with interesting structures having potential applications in organic chemistry, coordination chemistry, and the materials and biological sciences. A novel octanuclear nickel(II)–molybdenum(VI) heterometallic cluster based on the salicylhydroxamate ligand, namely di‐μ₃‐acetato‐di‐μ₂‐acetato‐di‐μ₃‐hydroxido‐di‐μ₃‐oxido‐tetraoxidooctakis(pyridine‐κN)bis(μ₅‐salicylhydroxamato)hexanickel(II)dimolybdenum(VI) monohydrate, [Mo₂Ni₆(C₇H₄NO₃)₂(C₂H₃O₂)₄O₅(OH)₂(C₅H₅N)₈]·H₂O, (I), was synthesized by the reaction of sodium molybdate, nickel acetate and salicylhydroxamic acid in a dimethylformamide/pyridine/methanol solution at room temperature. The salicylhydroxamate(3−) (shi³⁻), acetate and oxide ligands adopt complicated coordination modes and link six Ni^II and two Mo^VI cations into the octanuclear heterometallic cluster. All of the metal cations exhibit octahedral coordination geometries and are connected to each other through the sharing of corners, edges or planes. The heterometallic clusters are further connected to form two‐dimensional supramolecular layers through weak C—H…O hydrogen bonds. Studies of the magnetic properties of the title compound reveal antiferromagnetic interactions between the Ni^II cations.     

A cyanide‐bridged heterometallic coordination polymer constructed from square‐planar [Ni(CN)4]2−: synthesis,crystal structure,thermal decomposition,electron paramagnetic resonance (EPR) spectrum and magnetic properties

Square‐planar complexes are commonly formed by transition metal ions having a d⁸ electron configuration. Planar cyanometallate anions have been used extensively as design elements in supramolecular coordination systems. In particular, square‐planar tetracyanometallate(II) ions, i.e. [M(CN)₄]²⁻ (M^II = Ni, Pd or Pt), are used as good building blocks for bimetallic Hofmann‐type assemblies and their analogues. Square‐planar tetracyanonickellate(II) complexes have been extensively developed with N‐donor groups as additional co‐ligands, but studies of these systems using O‐donor ligands are scarce. A new cyanide‐bridged Cu^II–Ni^II heterometallic compound, poly[[diaquatetra‐μ₂‐cyanido‐κ⁸C:N‐nickel(II)copper(II)] monohydrate], {[Cu^IINi^II(CN)₄(H₂O)₂]·H₂O}_n, has been synthesized and characterized by X‐ray single‐crystal diffraction analyses, vibrational spectroscopy (FT–IR), thermal analysis, electron paramagnetic resonance (EPR) and magnetic moment measurements. The structural analysis revealed that it has a two‐dimensional grid‐like structure built up of cationic [Cu(H₂O)₂]²⁺ and anionic [Ni(CN)₄]²⁻ units connected through bridging cyanide ligands. The overall three‐dimensional supramolecular network is expanded by a combination of interlayer O—H…N and intralayer O—H…O hydrogen‐bond interactions. The first decomposition reactions take place at 335 K under a static air atmosphere, which illustrates the existence of guest water molecules in the interlayer spaces. The electron paramagnetic resonance (EPR) spectrum confirms that the Cu^II cation has an axial coordination symmetry and that the unpaired electrons occupy the d orbital. In addition, magnetic investigations showed that antiferromagnetic interactions exist in the Cu^II atoms through the diamagnetic [Ni(CN)₄]²⁻ ion.     

氰根和酚氧桥联M(Ⅱ)-Mn(Ⅲ)(M=Ru和Os)二维配合物的合成、结构与磁性

基于六氰根构筑单元[M（Ⅱ）（CN）₆]^4-与[Mn（Ⅲ）（salen）]⁺模块反应合成了2个新型酚氧和氰根混合桥联的M（Ⅱ）-Mn（Ⅲ）配合物{[Mn（Ⅲ）（salen）]₄[Mn（Ⅲ）（salen）（H₂O）]₂[M（Ⅱ）（CN）₆]}（ClO₄）₂·2H₂O（M=Ru （1）,Os （2）,salen^2-=双水杨酰胺乙基负离子）。单晶衍射结果表明：它们是结构类似的二维化合物,其中氰根桥联的七核[Mn（Ⅲ）₆M（Ⅱ）]²⁺单元进一步通过双酚氧桥相互连接构成二维层状结构。磁性研究表明：2个化合物通过酚氧桥均呈现反常的反铁磁耦合,基于自旋哈密顿算符Ĥ=-2J_MnMnŜ_Mn1Ŝ_Mn2拟合得到它们的磁耦合常数分别是J=-0.340 cm^-1 （1）和-0.561 cm^-1 （2）。     

Ba2+掺杂钙钛矿Bi0.5Ca0.5MnO3多晶材料的结构、磁性和输运性质研究

本文系统地研究了具有电荷有序(CO)和C型反铁磁(AFM)磁结构的钙钛矿锰氧化物Bi0.5Ca0.5-xBaxMnO3(x=0,0.03,0.05,0.07 and 0.10)的结构、磁性和电输运性质.系统晶格对称性保持Pnma空间群正交结构不变.随着Ba掺杂浓度的提高,电荷有序转变温度和反铁磁转变温度明显降低,表明掺...     

IrMn基反铁磁自旋阀的巨磁电阻效应

用第一性原理方法研究了在微观尺度具有三重对称磁结构的IrMn合金的反铁磁自旋阀(AFSV)的电子输运.研究表明:基于有序L1₂相IrMn合金的Co/Cu/IrMn自旋阀的巨磁电阻(GMR)效应具有三重对称性,可以利用这一特性区分反铁磁材料的GMR与传统铁磁材料的GMR.基于无序γ相IrMn合金的IrMn(0.84 nm)/Cu(0.42 nm)/IrMn(0.42 nm)/Cu(0.42 nm)(111) AFSV的电流平行平面构型的GMR约为7.7％,大约是电流垂直平面构型的GMR(3.4％)的两倍,明显大于实验中观测到的基于共线磁结构的FeMn基AFSV的GMR. 关键词： 反铁磁自旋阀 巨磁电阻效应 非共线磁结构 电流平行平面结构     

Crystal Structure,Thermal Behavior and Magnetic Properties of a New Copper（Ⅱ） Complex Based on Biphenyl-2,5,2＇,5＇-tetracarboxylic Acid

A new coordination polymer,[Cu2(bptc)(2,2'-bpy) 2(H2O)]·H2O(2,2'-bpy = 2,2'-bipyridine,H4bptc = biphenyl-2,5,2',5'-tetracarboxylic acid) ,has been synthesized under hydrother-mal conditions. The structure was characterized by single-crystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis. It crystallizes in triclinic,space group P1 with a = 10.6447(12) ,b = 11.0191(12),c = 16.1253(18) ,α = 79.538(2),β = 88.0720(10) ,γ = 61.6650(10) °,V = 1634.1(3) 3,C36H26Cu2N4O10,Mr = 801.69,Z = 2,Dc = 1.629 g/cm3,μ(MoKα) = 1.370 mm-1,F(000) = 816.0,R = 0.0418 and wR = 0.1135 for 4416 observed reflections with I > 2σ(I) . X-ray analysis shows that the title complex exhibits 1D wavelike [Cu2(bptc) ]n chains with two types of diamond-shaped pores. These 1D chains are linked into a 3D supramolecular structure via O-H···O,C-H···O interactions and weak π···π stacking interactions. There exist H-bonded helices in a right-and left-handed sequence by turns in a 2D layer. Moreover,thermal stability has been studied and magnetic measurements show antiferromagnetic interactions for this complex.     

Single-molecule magnet behaviour in a tetrathiafulvalene-based electroactive antiferromagnetically coupled dinuclear dysprosium(III) complex

The reactions between the [Ln(tta)(3)]·2H(2)O precursors (tta(-)=2-thenoyltrifluoroacetonate anion) and the tetrathiafulvalene-3-pyridine-N-oxide ligands (L(1)) lead to dinuclear complexes of formula [{Ln(tta)(3)(L(1))}(2)]·xCH(2)Cl(2) (x=0.5 for Ln=Dy(III) (1) and x=0 for Ln=Gd(III) (2)). The crystal structure reveals that two {Ln(tta)(3)} moieties are bridged by two donors through the nitroxide groups. The Dy(III) centre adopts a distorted square antiprismatic oxygenated polyhedron structure. The antiferromagnetic nature of the exchange interaction between the two Dy(III) ions has been determined by two methods: 1) an empirical method using the [Dy(hfac)(3)(L(2))(2)] mononuclear complex as a model (3) (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, L(2)=tetrathiafulvaleneamido-2-pyridine-N-oxide ligand), and 2) assuming an Ising model for the Dy(III) ion giving an exchange energy of -2.30 cm(-1), g=19.2 in the temperature range of 2-10 K. The antiferromagnetic interactions have been confirmed by a quantitative determination of J for the isotropic Gd(III) derivative (J=-0.031 cm(-1), g=2.003). Compound 1 displays a slow magnetisation relaxation without applied external magnetic fields. Alternating current susceptibility shows a thermally activated behaviour with pre-exponential factors of 5.48(4)×10(-7) s and an energy barrier of 87(1) K. The application of an external field of 1.6 kOe compensates the antiferromagnetic interactions and opens a new quantum tunnelling path.     

多铁性铬氧化物YCrO3体系的磁特性及比热研究

系统研究了低温条件下铬氧化物YCrO3体系的磁特性及比热特点.实验结果表明,在高温区(T＞140 K)直流磁化率随温度的变化遵从居里-外斯定律,YCrO3体系处于顺磁状态,样品的有效平均磁矩μefr=3.99μB、顺磁居里-外斯温度TCw =-340 K,即体系具有反铁磁性.在TN =140 K附近,YCrO3体系经历了由顺磁态向倾角反铁磁态的相转变,其自旋磁结构一直保持为Г4(Gx,Ay,Fz;FRz);低温条件下(T＜140 K),体系具有完整闭合的磁滞回线,表明YCrO3样品具有反铁磁性的同时,具有明显的弱铁磁性,且随温度的降低铁磁性逐渐增强.对应于磁相变温度TN,比热曲线在140 K附近出现尖锐的λ形反常突起,由于Y离子没有磁性,显示了Cr3+磁矩亚晶格的顺磁-反铁磁相变对比热的贡献.