A Ni2+ (S = 1) Kagome compound templated by 1,4-diazacubane [corrected

1,8-Diazacubane-templated nickel(II) sulfate with the Kagome structure prepared under solvothermal conditions exhibits interesting magnetic properties.     

Role of the spin magnitude of the magnetic ion in determining the frustration and low-temperature properties of kagome lattices

In view of the variety of low-temperature magnetic properties reported recently for kagome lattices with transition-metal ions in different oxidation states, we have investigated the low-energy spectrum and low-temperature thermodynamic properties of antiferromagnetic kagome lattices with varying magnitudes of site spins, employing quantum many-body Heisenberg models. The ground state and the low-lying excitation spectrum are found to depend strongly on the nature of the spin magnitude of the magnetic ions. The system remains highly frustrated if spins are half-odd-integer in magnitude, while the frustration is very weak or almost absent for integer spins or mixed-spin systems. In fact, for a mixed-spin kagome system with a certain magnitude, the whole system behaves as a classical magnet with a ferrimagnetic ground state without any frustration. These theoretical findings are consistent with a few experimental observations recently reported in the literature and would be of value in designing new kagome systems with unusual and interesting low-temperature magnetic properties.     

Synthesis and magnetic properties of an amine-templated Fe2+ (s = 2) sulfate with a distorted Kagome structure

An organically templated iron(II) sulfate of the composition [H3N(CH2)2NH2(CH2)2(NH3]4[Fe(II)9F18(SO4)6].9H2O with a distorted Kagome structure has been synthesized under solvothermal conditions in the presence of diethylenetriamine. The distortion of the hexagonal bronze structure comes from the presence of two different types of connectivity between the FeF4O2 octahedra and the sulfate tetrahedra. This compound exhibits magnetic properties different from those of an Fe(II) compound with a perfect Kagome structure and is a canted antiferromagnet at low temperatures.     

Effects of frustration on magnetic molecules: a survey from Olivier Kahn until today

In magnetism, of which molecular magnetism is a part, the term frustration is used rather sloppily. Sometimes one gains the impression that if the reason for some phenomenon is not quite clear then it is attributed to frustration. In this paper a discussion of the effects of frustration that are relevant for the field of molecular magnetism is presented. As will become clear later these effects indeed lead to a variety of unusual magnetic properties.     

Electronic structure and magnetic properties of small manganese oxide clusters

To investigate the electronic structure and magnetic properties of manganese oxide clusters, we carried out first-principles electronic structure calculations for small MnO clusters. Among various structural and magnetic configurations of the clusters, the bulklike [111]-antiferromagnetic ordering is found to be favored energetically, while the surface atoms of the clusters exhibit interesting electronic and magnetic characteristics which are different from their bulk ones. The distinct features of the surface atoms are mainly attributed to the reduction of Mn coordination numbers and the bond-length contractions in the clusters, which may serve as a key factor for the understanding of physical and chemical properties of magnetic oxide nanoparticles.     

A three-dimensional metal-organic framework with a distorted Kagome related layer showing canted antiferromagnetic behaviour

Three-dimensional [Mn(3){C(6)H(3)(COO)(3)}(2)] comprising two-dimensional -Mn-O-Mn- distorted Kagome layers, formed by two geometrically different hexa-coordinated Mn(2+) ions, show less frustration and spin canted long range ordering possibly due to antisymmetric exchange.     

Topotactic oxidative and reductive control of the structures and properties of layered manganese oxychalcogenides

Topotactic modification, by both oxidation and reduction, of the composition, structures, and magnetic properties of the layered oxychalcogenides Sr4Mn3O7.5Cu2Ch2 (Ch=S, Se) is described. These Mn3+ compounds are composed of alternating perovskite-type strontium manganese oxide slabs separated by anti-fluorite-type copper chalcogenide layers and are intrinsically oxide deficient in the central layer of the perovskite slabs. The systems are unusual examples of perovskite-related compounds that may topotactically be both oxidized by fluorination and reduced by deintercalation of oxygen from the oxide-deficient part of the structure. The compounds exhibit antiferromagnetic ordering of the manganese magnetic moments in the outer layers of the perovskite slabs, while the other moments, in the central layers, exhibit spin-glass-like behavior. Fluorination has the effect of increasing the antiferromagnetic ordering temperature and the size of the ordered moment, whereas reduction destroys magnetic long-range order by introducing chemical disorder which leads to both further disorder and frustration of the magnetic interactions in the manganese oxide slab.     

Size dependence of the magnetic properties in ferrimagnetic rings MnxRx (x = 2–8)

Size dependence of the magnetic properties in nanoscale ferrimagnetic rings is investigated by the numerical diagonalization of the Heisenberg model. The field derivative of the magnetization is drastically dependent on size of the ring if the magnetic system has frustration, although the character does not exist in the non-frustrated system. Our numerical data support this tendency that the effect of frustration causes the size dependence of the magnetic properties in the nanoscale ferrimagnetic ring. We also demonstrate that the size dependence caused by frustration is also found in behavior of the translational quantum number of the ground state.     

An organically templated iron sulfate with a distorted Kagome lattice exhibiting unusual magnetic properties

A layered iron sulfate of the composition [H3N(CH2)2NH2(CH2)2NH2(CH2)2NH3][FeII3F6(SO4)2], possessing a distorted Kagome lattice, prepared hydrothermally, is found to exhibit magnetic hysteresis like a ferrimagnet besides the characteristics of a frustrated system, like those of a spin glass.     

Inorganic-organic hybrid framework solids

Recent developments in the area of hybrid structures are overviewed with special emphasis on iron phosphate-oxalate materials. The structure of the iron phosphate-oxalates consists of iron phosphate chains or layers that are connected by oxalate moieties completing the architecture. The compounds exhibit interesting magnetic properties originating from the super-exchange interactions that are predominantly anti-ferromagnetic, involving the iron phosphates and the oxalate moieties. One of the materials,IV, also exhibits interesting adsorptive properties reminiscent of aluminosilicate zeolites. The aluminum phosphate-oxalate,VII, indicates that hybrid structures can be formed with zeolite architecture.     

ZnSe: Fe2+中的动态Jahn-Teller效应和远红外光谱的研究

推导了3d4/3d6离子基态 5D在立方晶体场、自旋-轨道耦合和动态Jahn-Teller效应作用下的哈密顿矩阵,并用对角化该哈密顿矩阵的方法研究了Fe2+在ZnSe中的远红外光谱,理论计算与实验符合得好.研究表明,在ZnSe∶ Fe2+中,比晶体场理论分析多出的分裂谱线是Fe2+与ZnSe晶格间的动态Jahn-Teller效应引起的.还预测了其它Jahn-Teller效应分裂谱.所推导的哈密顿矩阵对研究3d4/3d6离子在立方晶体中的精细光谱、电子顺磁共振谱和动态Jahn-Teller分裂都是有用的.     

β‐Ag3RuO4, a Ruthenate(V) Featuring Spin Tetramers on a Two‐Dimensional Trigonal Lattice

Open‐shell solids exhibit a plethora of intriguing physical phenomena that arise from a complex interplay of charge, spin, orbital, and spin‐state degrees of freedom. Comprehending these phenomena is an indispensable prerequisite for developing improved functional materials. This type of understanding can be achieved, on the one hand, by experimental and theoretical investigations into known systems, or by synthesizing new solids displaying unprecedented structural and/or electronic features. β‐Ag₃RuO₄ may serve as such a model system because it possesses a remarkable anionic structure, consisting of tetrameric polyoxoanions (Ru₄O₁₆)^12?, and is an embedded fragment of a 2D trigonal MO₂ lattice. The notorious frustration of antiferromagnetic (AF) exchange couplings on such lattices is thus lifted, and instead strong AF occurs within the oligomeric anion, where only one exchange path remains frustrated among the relevant six. The strong magnetic anisotropy of the [Ru₄O₁₆]^12? ion, and the effectively orbital nature of its net magnetic moment, implies that this anion may reveal the properties of a single‐molecule magnet if well‐diluted in a diamagnetic matrix.     

Synthesis, structure and magnetic properties of an amine-templated Mn2+ (S = 5/2) sulfate with the Kagome structure

In pursuit of a compound with the Kagome structure, formed by a non-Fe(3+) transitional metal ion with a spin of 5/2, we have synthesized an amine-templated Mn(2+) sulfate under solvothermal conditions. This compound with a perfect Kagome structure shows evidence for antiferromagnetic interactions with no long-range order.     

Folding behavior of model proteins with weak energetic frustration

The native structure of fast-folding proteins, albeit a deep local free-energy minimum, may involve a relatively small energetic penalty due to nonoptimal, though favorable, contacts between amino acid residues. The weak energetic frustration that such contacts represent varies among different proteins and may account for folding behavior not seen in unfrustrated models. Minimalist model proteins with heterogeneous contacts--as represented by lattice heteropolymers consisting of three types of monomers--also give rise to weak energetic frustration in their corresponding native structures, and the present study of their equilibrium and nonequilibrium properties reveals some of the breadth in their behavior. In order to capture this range within a detailed study of only a few proteins, four candidate protein structures (with their cognate sequences) have been selected according to a figure of merit called the winding index--a characteristic of the number of turns the protein winds about an axis. The temperature-dependent heat capacities reveal a high-temperature collapse transition, and an infrequently observed low-temperature rearrangement transition that arises because of the presence of weak energetic frustration. Simulation results motivate the definition of a new measure of folding affinity as a sequence-dependent free energy--a function of both a reduced stability gap and high accessibility to non-native structures--that correlates strongly with folding rates.     

Preparation and magnetic properties of RFeO<Subscript>3</Subscript> nanocrystalline powders

The rare-earth orthoferrites RFeO₃ (R, rare-earth element) crystallize in an orthorhombic distorted perovskite structure. RFeO₃ compounds exhibit interesting physical and chemical properties because of their ionic and electronic defects. Polycrystalline nano-sized RFeO₃ powders were synthesized by the sol–gel combustion method. X-ray powder diffraction indicated that nanocrystalline powders were single ReFeO3 phase, which are agglomerated with average crystallite size of 60–90 nm estimated with the Scherrer’s equation. Magnetic measurements were carried out using a superconducting quantum interference device magnetometer. The influence on hysteresis curve of electronic structure of rare-earth element was investigated for R = Y, La and Nd. Varied magnetic behaviors were observed in these compounds, which are believed to be associated with the different interactions of Fe and rare earths.     

Evidence of a Mixed Magnetic Phase in EuMgGe: A Semi­metallic Zintl Compound with TiNiSi Structure Type

The ternary Zintl phase EuMgGe was synthesized from the elements, and its structure solved by single‐crystal X‐ray diffraction. Chemical bonding is discussed, by means of electronic structure calculations at the DFT level and its physical properties characterized with respect to electronic conductivity, magnetic susceptibility, specific heat capacity, and magnetoresistivity. The compound may be interpreted according to the Zintl‐Klemm concept as (Eu²⁺)(Mg²⁺)(Ge^4–) with isolated germanium anions. Resistivity measurements reveal a semimetallic character, which is consistent with the vanishing energy gap obtained from our calculations. The magnetic susceptibility and the specific heat indicate that two consecutive transitions take place, at 9 and 16 K, and they show evidence of magnetic frustration. A possible physical scenario for this magnetic behavior is discussed based on known models of partially frustrated magnets.     

Electrochemical Properties of Vanadium Oxide Aerogels and Aerogel Nanocomposites

The electrochemical properties of high surface area transition metal oxide aerogels are extremely interesting because aerogels serve to amplify surface effects. As a result, the electrochemical properties are dominated by surfaces rather than by bulk behavior. In the case of vanadium oxide aerogels this leads to extraordinary electrochemical properties, including an extremely high capacity for lithium and electrochemical responses that are both battery-like and capacitor-like. By exploiting sol-gel synthesis, it is possible to synthesize nanocomposite electrodes in which aerogels are in intimate contact with carbon nanotubes. The resulting nanocomposites exhibit superior electrochemical properties, especially at high discharge.     

The pyrochlore family -- a potential panacea for the frustrated perovskite chemist

Many known complex oxides of general formula A(2)B(2)X(7) adopt the pyrochlore structure, a key structure-type that has been shown to demonstrate a vast range of useful physical properties. Areas currently of much interest with respect to pyrochlores, include metal-insulator transitions, magnetic frustration/spin ices, magnetoresistance, superconductivity, ferroelectrics, O/F ionic conductivity, mixed conductivity, pigments and catalysis. We present some recent results on three types of pyrochlore materials that show unusual magnetic, optical and electronic behaviours associated with subtle structural and compositional changes. High-resolution powder neutron diffraction studies of the superconducting Cd(2)Re(2)O(7) and the ferroelectric Cd(2)Nb(2)O(7) have been undertaken on material cooled below room temperature. Both Cd(2)Re(2)O(7) and Cd(2)Nb(2)O(7) exhibit small structure distortions, in each case involving a distortion from a cubic unit cell, on cooling below approximately 180 K and possible models that can be used to describe the low-temperature structures and associated atomic displacements are developed and described in this article. A range of materials of the general formula Ca(1-x)Ln(x)TaO(2-x)N(1+x), x= 0.5 and x= 1, Ln = La-Yb have been synthesised and shown to adopt pyrochlore and/or perovskite structures. The absorption spectra of these materials are discussed in terms of their structures and compositions.     

Thermodynamic properties of non-conformal soft-sphere fluids with effective hard-sphere diameters

In this work we study a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids. This type of soft spheres is of interest because they represent quite accurately the effective intermolecular repulsion in fluid substances and also because they exhibit interesting properties. The thermodynamics of the soft-sphere fluids is obtained via an effective hard-sphere diameter approach that leads to a compact and accurate equation of state. The virial coefficients of soft spheres are shown to follow quite simple relationships that are incorporated into the equation of state. The approach followed exhibits the rescaling of the density that produces a unique equation for all systems and temperatures. The scaling is carried through to the level of the structure of the fluids.     

Spin dimer analysis of the anisotropic spin exchange interactions in the distorted wolframite-type oxides CuWO4, CuMoO4-III, and Cu(Mo(0.25)W0.75)O4

The distorted wolframite-type oxides CuWO4 and CuMoO4-III have a structure in which CuO4 zigzag chains, made up of cis-edge-sharing CuO6 octahedra, run along the c-direction and hence exhibit low-dimensional magnetic properties. We examined the magnetic structures of these compounds and their isostructural analogue Cu(Mo(0.25)W0.75)O4 on the basis of the spin-orbital interaction energies calculated for their spin dimers. Our study shows that these compounds consist of two-dimensional (2D) magnetic sheets defined by one superexchange (intrachain Cu-O-Cu) and three super-superexchange (interchain Cu-O.O-Cu) paths, the strongly interacting spin units of these 2D magnetic sheets are the two-leg antiferromagnetic (AFM) ladder chains running along the (a + c)-direction, and the spin arrangement between adjacent AFM ladder chains leads to spin frustration. The similarities and differences in the magnetic structures of CuWO4, CuMoO4-III, and Cu(Mo(0.25)W0.75)O4 were discussed by examining how adjacent AFM ladder chains are coupled via the superexchange paths in the 2D magnetic sheets and how adjacent 2D magnetic sheets are coupled via another superexchange paths along the c-direction. Our study reproduces the experimental finding that the magnetic unit cell is doubled along the a-axis in CuWO(4) and along the c-axis in CuMoO4-III and predicts that the magnetic unit cell should be doubled along the a- and b-axes in Cu(Mo(0.25)W0.75)O4. In the understanding of the strength of a super-superexchange interaction, the importance of the geometrical factors controlling the overlap between the tails of magnetic orbitals was pointed out.