锂离子电池富锂正极材料Li[NixLi1/3-2x/3Mn2/3-x/3]O2(x=1/5, 1/4, 1/3)的合成及电化学性能

通过共沉淀法制备了M(OH)2(M=Mn, Ni)前驱体, 并与LiOH混合, 合成了锂离子电池富锂正极材料Li[NixLi1/3-2x/3Mn2/3-x/3]O2, 采用XRD、SEM和充放电实验对其进行表征. 研究结果表明, Li, Ni, Mn原子在M层中呈有序分布, 形成超结构; 富锂正极材料由亚微米的一次粒子团聚组成1~3 μm颗粒; 在2.0~4.8 V电位范围内, 充放电电流密度为10 mA/g时, 富锂正极材料表现出很高的可逆比容量, 达到200~240 mA·h/g, 同时具有良好的循环可逆性能.     

Syntheses，Structures and Properties of Some New Composition Perovskite Compounds：Sr_（0．6）Bi_（0．4）FeO_（2．7），Sr_（1－x）Bi_xFeO_（3－y） and Ba_（1．5）Pt_（0．5）Mn_2O_6

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Polarization Rotation in the Monoclinic Perovskite BiCo(1-x) Fe(x) O(3)

The monoclinic perovskite BiCo(1-x) Fe(x) O(3) (x≈0.7) undergoes a second-order structural transition from tetragonal to monoclinic, which is accompanied by a rotation of the polarization vector from the [001] to [111] directions of a pseudo cubic cell. The crystal structure, determined by electron diffraction and powder synchrotron X-ray diffraction, was the same as that of Pb(Ti(1-x) Zr(x) )O(3) at the morphotropic phase boundary.     

Covalent metal-organic networks: pyridines induce 2-dimensional oligomerization of (mu-OC6H4O)2Mpy2 (M = Ti, V, Zr)

Treatment of M(OiPr)4 (M = Ti, V) and [Zr(OEt)4]4 with excess 1,4-HOC6H4OH in THF afforded [M(OC6H4O)a(OC6H4OH)3.34-1.83a(OiPr)0.66-0.17a(THF)0.2]n (M = Ti, 1-Ti; V, 1-V, 0.91 < or = a < or = 1.82) and [Zr(1,4-OC6H4O)2-x(OEt)2x]n (1-Zr, x = 0.9). The combination of of 1-M (M = Ti, V, Zr) or M(OiPr)4 (M = Ti, V), excess 1,4- or 1,3-HOC6H4OH, and pyridine or 4-phenylpyridine at 100 degrees C for 1 d to 2 weeks afforded various 2-dimensional covalent metal-organic networks: [cis-M(mu 1,4-OC6H4O)2py2] infinity (2-M, M = Ti, Zr), [trans-M(mu 1,4-OC6H4O)2py2.py] infinity (3-M, M = Ti, V), solid solutions [trans-TixV1-x(mu 1,4-OC6H4O)2py2.py] infinity (3-TixV1-x, x approximately 0.4, 0.6, 0.9), [trans-M(mu 1,4-OC6H4O)2(4-Ph-py)2] infinity (4-M, M = Ti, V), [trans-Ti(mu 1,3-OC6H4O)2py2] infinity (5-Ti), and [trans-Ti(mu 1,3-OC6H4O)2(4-Ph-py)2] infinity (6-Ti). Single-crystal X-ray diffraction experiments confirmed the pleated sheet structure of 2-Ti, the flat sheet structure of 3-Ti, and the rippled sheet structures of 4-Ti, 5-Ti, and 6-Ti. Through protolytic quenching studies and by correspondence of powder XRD patterns with known titanium species, the remaining complexes were structurally assigned. With py or 4-Ph-py present, aggregation of titanium centers is disrupted, relegating the building block to the cis- or trans-(ArO)4Tipy2 core. The sheet structure types are determined by the size of the metal and the interpenetration of the layers, which occurs primarily through the pyridine residues and inhibits intercalation chemistry.     

Core-shell microspherical Ti(1-x)Zr(x)O2 solid solution photocatalysts directly from ultrasonic spray pyrolysis

A series of Ti(1-x)Zr(x)O(2) solid solutions photocatalysts (x = 0.000, 0.045, 0.090, 0.135, and 0.180) was directly obtained by an ultrasonic spray pyrolysis method. Compared with previous methods for solid solutions, our preparation was very fast. The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, nitrogen adsorption, and UV-vis diffuse reflectance spectroscopy. The characterizations revealed core-shell spherical structures of the resulting solid solutions. We evaluated photocatalytic activities of the solid solutions on degradation of rhodamine B in aqueous solution under simulated solar light. It was found that Ti(0.91)Zr(0.09)O(2) solid solution exhibited the highest photocatalytic activity among all the as-prepared samples. Its activity was much higher than that of P25. The formation mechanism of core-shell spherical structures was proposed. Moreover, we successfully extended this method to prepare microspheres of ceria and ceria-zirconia solid solutions. We think this general method may be easily scaled up for industrial production of microspherical solid solutions photocatalysts and catalysts.     

Influence of disorder-to-order transition on lattice thermal expansion and oxide ion conductivity in (Ca(x)Gd(1-x))(2)(Zr(1-x)M(x))2O7 pyrochlore solid solutions

The effect of simultaneous substitutions of Ca at A site and Nb or Ta at B site in pyrochlore-type solid solutions: (Ca(x)Gd(1-x))(2)(Zr(1-x)M(x))(2)O(7) (x = 0.1, 0.2, 0.3, 0.4, 0.5 and M = Nb or Ta) were studied by powder X-ray diffraction (XRD), FT NIR Raman spectroscopic techniques and transmission electron microscopy. The solid solutions were prepared by the conventional high-temperature ceramic route. The XRD results and Rietveld analysis revealed that the defect fluorite structure of Gd(2)Zr(2)O(7) progressively changed to a more ordered pyrochlore phase by simultaneous substitutions at A and B sites. Raman spectroscopy reveals the progressive ordering in the anion sublattice with simultaneous doping. High-resolution images and selected-area electron diffraction patterns obtained from TEM confirms the XRD and Raman spectroscopic results. High-temperature XRD studies show that the lattice expansion coefficient in these pyrochlore oxides is of the order of 10(-6) K(-1). Lattice thermal expansion coefficient increases with increase of disorder in pyrochlore oxides, and hence the variation of thermal expansion coefficient with composition is also a good indicator of disordering in pyrochlore-type oxides. The ionic conducting properties of the samples were characterised by impedance spectroscopy, and it was found that Nb-doped compositions show a considerable change in conductivity near the phase boundary of disordered pyrochlore and defect fluorite phases.     

A variable Ag-Cr-Oxalate channel lattice: [M(x)Ag(0.5)(-)(x)(H(2)O)(3)]@[Ag(2.5)Cr(C(2)O(4))(3)], M = K, Cs, Ag

Reaction of aqueous AgNO(3) with aqueous M(3)[Cr(ox)(3)] in >or=3:1 molar ratio causes the rapid growth of large, cherry-black, light-stable crystals which are not Ag(3)[Cr(ox)(3)], but [M(0.5)(H(2)O)(3)]@[Ag(2.5)Cr(ox)(3)] (ox(2)(-) = oxalate, C(2)O(4)(2)(-); M = Na, K, Cs, Ag, or mixtures of Ag and a group 1 element). The structure of these crystals contains an invariant channeled framework, with composition [[Ag(2.5)Cr(ox)(3)](-)(0.5)]( infinity ), constructed with [Cr(ox)(3)] coordination units linked by Ag atoms through centrosymmetric [Cr-O(2)C(2)O(2)-Ag](2) double bridges. The framework composition [Ag(2.5)Cr(ox)(3)](-)(0.5) occurs because one Ag is located on a 2-fold axis. Within the channels there is a well-defined and ordered set of six water molecules, strongly hydrogen bonded to each other and some of the oxalate O atoms. This invariant channel plus water structure accommodates group 1 cations, and/or Ag cations, in different locations and in variable proportions, but always coordinated by channel water and some oxalate O atoms. The general formulation of these crystals is therefore [M(x)Ag(0.5-x)(H(2)O)(3)]@[Ag(2.5)Cr(ox)(3)]. Five different crystals with this structure are reported, with compositions 1 Ag(0.5)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 2 Cs(0.19)Ag(0.31)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 3 K(0.28)Ag(0.22)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 4 Cs(0.41)Ag(0.09)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), and 5 Cs(0.43)Ag(0.07) [Ag(2.5)Cr(ox)(3)](H(2)O)(3). All crystallize in space group C2/c, with a approximately 18.4, b approximately 14.6, c approximately 12.3 A, beta approximately 113 degrees. Pure Ag(3)[Cr(ox)(3)](H(2)O)(3), which has the same crystal structure (1), was obtained from water by treating Li(3)[Cr(ox)(3)] with excess AgNO(3). Complete dehydration of all of these compounds occurs between 30 and 100 degrees C, with loss of diffraction, but rehydration by exposure to H(2)O(g) at ambient temperature leads to recovery of the original diffraction pattern. In single crystals, this reversible dehydration-hydration occurs without visually evident crystal change, but with loss of mechanical strength. We postulate a general mechanism for transport of water molecules along the channels, associated with local partial collapses of the channel framework, with concomitant bending but little breaking of the host Ag-O and Cr-O bonds, which is readily reversed.     

Phase relations and crystal structures in the system Ta-V-Ge

Phase equilibria have been derived for the isothermal section of the Ta-V-Ge system at 1500 °C (for concentrations <45 at% Ge) on the basis of X-ray powder diffraction, EPMA and TEM analyses of argon arc melted alloys annealed in high vacuum at 1500 °C up to 200 hours. Four ternary phases have been identified within the isothermal section, out of which three were characterized by Rietveld refinement of X-ray powder diffraction data. τ(1)-(Ta(1-x)V(x))(5)Ge(3) (0.21 ≤ x ≤ 0.63) adopts the Mn(5)Si(3)-type and τ(2)-Ta(Ta(x)V(1-x-y)Ge(y))(2), x = 0.02, y = 0.12 was found to be a MgZn(2)-type Laves phase. Detailed transmission electron microscopy (TEM) in several crystallographic directions confirmed lattice parameters and crystal symmetry of this phase and rejected the presence of any superstructure. τ(3)-Ta(9-x+y)V(4+x-y-z)Ge(1+z), x = 0.32, y = 0.51, z = 0.98 crystallizes with the Nb(9)Co(4)Ge-type, whereas the structure of τ(4) is not yet known. Although a MgCu(2)-type cubic Laves phase is not present in the Ta-V binary at this temperature, additions of Ge stabilize this phase in the ternary system: C15-Ta(Ta(x)V(1-x-y)Ge(y))(2), x = 0.04, y = 0.05. V(11)Ge(8) (Cr(11)Ge(8) type) shows a large solubility up to (Ta(x)V(1-x))(11)Ge(8), x = 0.64 at 1500 °C.     

Cubic form of Pb(2-x)Sn(x)S2 stabilized through size reduction to the nanoscale

We demonstrate the synthesis of semiconductor Pb(2-x)Sn(x)S(2) nanocrystals with a cubic rock salt crystal structure in a composition range where this structure is unstable in the bulk. The cubic Pb(2-x)Sn(x)S(2) nanocrystals were prepared using a modified hot injection colloidal synthetic route. The x value is in the range 0.40 < x < 1. Even though these compositions lie in a region of the PbS-SnS phase diagram where no single phase exists, and despite the fact that PbSnS(2) is a distorted orthorhombic phase, the Pb(2-x)Sn(x)S(2) nanocrystals are single phase solid solutions with cubic NaCl-type structure. Experimental evidence for this derives from powder X-ray diffraction (PXRD), electron diffraction, and pair distribution function (PDF) analysis. Elemental compositions determined using scanning transmission electron microscopy/energy dispersive spectroscopy (STEM/EDS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and electron energy loss spectroscopy (EELS) reveal a composition close to the nominal ones. The band gaps of the Pb(2-x)Sn(x)S(2) nanocrystals (0.52-0.57 eV) are blue-shifted by quantum confinement relative to that of the hypothetical cubic PbSnS(2) phase which density functional theory (DFT) calculations show to be much narrower (0.2 eV) than in the case of orthorhombic PbSnS(2) (1.1 eV). The Pb(2-x)Sn(x)S(2) nanocrystals exhibit a well-defined band gap in the near-IR region and are stable up to ~300 °C above which they phase separate into cubic PbS and orthorhombic α-SnS.     

Nanostructuring, compositional fluctuations, and atomic ordering in the thermoelectric materials AgPb(m)SbTe(2+m). The myth of solid solutions

The nature of the thermoelectric materials Ag(1-x)Pb(m)SbTe(m+2) or LAST-m materials (LAST for Lead Antimony Silver Tellurium) with different m values at the atomic as well as nanoscale was studied with powder/single-crystal X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy. Powder diffraction patterns of different members (m = 0, 6, 12, 18, infinity) are consistent with pure phases crystallizing in the NaCl-structure-type (Fmm) and the proposition that the LAST family behaved as solid solutions between the PbTe and AgSbTe2 compounds. However, electron diffraction and high resolution transmission electron microscopy studies suggest the LAST phases are inhomogeneous at the nanoscale with at least two coexisting sets of well-defined phases. The minority phase which is richer in Ag and Sb is on the nanosized length scale, and it is endotaxially embedded in the majority phase which is poorer in Ag and Sb. Moreover, within each nanodomain we observe extensive long range ordering of Ag, Pb, and Sb atoms. The long range ordering can be confirmed by single crystal X-ray diffraction studies. Indeed, data collections of five different single crystals were successfully refined in space groups of lower symmetry than Fmm including P4/mmm and Rm. The results reported here provide experimental evidence for a conceptual basis that could be employed when designing high performance thermoelectric materials and dispel the decades long belief that the systems (AgSbTe2)(1-x)(PbTe)x are solid solutions.     

Sandia octahedral molecular sieves (SOMS): structural and property effects of charge-balancing the M(IV)-substituted (M = Ti, Zr) Niobate framework

Sandia octahedral molecular sieves (SOMS) is an isostructural, variable composition class of ion exchangers with the general formula Na(2)Nb(2-x)M(IV)(x)O (6-x)(OH)(x).H(2)O (M(IV) = Ti, Zr; x = 0.04-0.40) where up to 20% of the framework Nb(V) can be substituted with Ti(IV) or Zr(IV). This class of molecular sieves is easily converted to perovskite through low-temperature heat treatment (500-600 degrees C). This report provides a detailed account of how the charge imbalance of this Nb(V)-M(IV) substitution is compensated. X-ray powder diffraction with Rietveld refinement, infrared spectroscopy, thermogravimetric analysis, (23)Na MAS NMR, and (1)H MAS NMR were used to determine how the framework anionic charge is cation-balanced over a range of framework compositions. All spectroscopic evidence indicated a proton addition for each M(IV) substitution. Evidences for variable proton content included (1) increasing OH observed by (1)H MAS NMR with increasing M(IV) substitution, (2) increased infrared band broadening indicating increased H-bonding with increasing M(IV) substitution, (3) increased TGA weight loss (due to increased OH content) with increasing M(IV) substitution, (4) no variance in population on the sodium sites (indicated by Rietveld refinement) with variable composition, and (5) no change in the (23)Na MAS NMR spectra with variable composition. Also observed by infrared spectroscopy and (23)Na MAS NMR was increased disorder on the Nb(V)/M(IV) framework sites with increasing M(IV) substitution, evidenced by broadening of these spectral features. These spectroscopic studies, along with ion exchange experiments, also revealed the effect of the Nb(V)/M(IV) framework substitution on materials properties. Namely, the temperature of conversion to NaNb(1-x)M(IV)(x)O(3) (M = Ti, Zr) perovskite increased with increasing Ti in the framework and decreased with increasing Zr in the framework. This suggested that Ti stabilizes the SOMS framework and Zr destabilizes the SOMS framework. Finally, comparing ion exchange properties of a SOMS material with minimal (2%) Ti to a SOMS material with maximum (20%) Ti revealed the divalent cation selectivity of these materials which was reported previously is a function of the M(IV) substitution in the framework. A thorough investigation of this class of SOMS materials has revealed the importance of understanding the influence of heterovalent substitutions in microporous frameworks on material properties.     

Comprehensive interpretation of a substitution effect on an order-disorder phase transition in A(1-x)MxW2O(8-y) (A = Zr, Hf; M = trivalent cations) and other ZrW2O8-based solid solutions

Hf(1-x)Lu(x)W(2)O(8-y) solid solutions up to x = 0.04, based on a negative thermal expansion material HfW(2)O(8), were synthesized by a solid state reaction method. X-ray diffraction experiments of these solid solutions from 90 to 560 K indicated thermal contraction with increasing temperature. Temperatures of order-disorder phase transition (T(trs)) associated with the orientation of WO(4) tetrahedra were determined from disappearance of a characteristic diffraction peak (310). The T(trs) of the solid solutions drastically decreased with increasing Lu content. Saturated order parameters (eta(s)) associated with the orientational order of the WO(4) pairs were estimated from the characteristic diffraction peak at sufficient low temperature. These behaviors of Hf(1-x)Lu(x)W(2)O(8-y) are consistent with those of Zr(1-x)M(x)W(2)O(8-y) (M = Sc, Y, In, Lu). The drastic suppression of T(trs) in Hf(1-x)Lu(x)W(2)O(8-y) can be interpreted in the framework of a model proposed for Zr(1-x)M(x)W(2)O(8-y), which states the existence of a local nanoregion including the WO(4) pairs having the frozen-in orientational disorder. To understand the substitution effect on the order-disorder phase transition comprehensively, classification based on the saturated order parameter eta(s) of the phase transition of AW(2)O(8) (A = Hf, Zr)-based solid solutions was carried out and discussed.     

Large-scale synthesis of single-crystalline RE2O3 (RE=Y, Dy, Ho, Er) nanobelts by a solid-liquid-phase chemical route

Yttrium-group heavy rare-earth sesquioxide (RE(2)O(3), RE=Y, Dy, Ho, Er) nanobelts were successfully fabricated by thermolysis of solid RE(NO(3))(3)x H(2)O in a dodecylamine/1-octadecene mixed solvent system. The synthetic principle is based on separating the nucleation and growth processes by utilizing the poor solubility of RE(NO(3))(3)chi H(2)O in the solvent mixture and the heat-transportation difference between the liquid and solid. By using dodecylamine, RE(2)O(3) nanobelts can be readily obtained. X-ray diffraction (XRD) analysis shows that the synthesized RE(2)O(3) nanobelts are body-centered cubic and crystalline. Field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), selective-area electron diffraction (SAED), and high-resolution transmission electron microscopy (HR-TEM) demonstrate that the synthesized RE(2)O(3) compounds possess regular geometric structure (beltlike) with perfect crystallinity. Preliminary experimental results prove that the dodecylamine plays a key role in the formation of RE(2)O(3) nanobelts and cannot be replaced by other surfactants. Furthermore, this method can be extended to the synthesis of RE(2)O(3) nanobelt/metal nanocrystal nanocomposites and ABO(3) (A=Y, Dy, Ho, Er; B=Al) and A(3)B(5)O(12) (A=Y, Dy, Ho, Er; B=Al)-type ternary oxide nanobelts, using mixed-metal nitrate salts in the correct stoichiometry instead of single rare-earth nitrates.     

Use of ionic liquids (ILs) for the IL-anion size-dependent formation of Cr, Mo and W nanoparticles from metal carbonyl M(CO)6 precursors

Stable chromium, molybdenum and tungsten nanoparticles are obtained reproducibly by thermal or photolytic decomposition under argon from mononuclear metal carbonyl precursors M(CO)(6) (M=Cr, Mo, W) suspended in the ionic liquids BMim(+)BF(4)(-), BMim(+)OTf(-) and BtMA(+)Tf(2)N(-) (BMim(+)=n-butyl-methyl-imidazolium, BtMA(+)=n-butyl-trimethyl-ammonium, Tf(2)N=N(O(2)SCF(3))(2), OTf=O(3)SCF(3)) with a very small and uniform size of 1 to 1.5 nm in BMim(+)BF(4)(-) which increases with the molecular volume of the ionic liquid anion to approximately 100 nm in BtMA(+)Tf(2)N(-) [characterization by transmission electron microscopy (TEM), dynamic light scattering and transmission electron diffraction (TED) analysis].     

K3[Tb(x)Eu(1-x)Ge3O8(OH)2] (x = 1, 0.88, 0.67, 0): 2D-layered lanthanide germanates with tunable photoluminescent properties

A family of novel 2D-layered lanthanide germanates K(3)[Tb(x)Eu(1-x)Ge(3)O(8)(OH)(2)] (x = 1, 0.88, 0.67, 0; denoted as TbGeO-JU-87, Tb(0.88)Eu(0.12)GeO-JU-87, Tb(0.67)Eu(0.33)GeO-JU-87, and EuGeO-JU-87) were synthesized under mild hydrothermal conditions in a concentrated gel system. They are isostructural, as confirmed by the powder X-ray diffraction analysis. The single-crystal X-ray diffraction analysis of EuGeO-JU-87 reveals that it is a 2D-layered [EuGe(3)O(8)(OH)(2)](n)(3n-) anionic framework, which is built up from GeO(4)H/GeO(4) tetrahedra and EuO(6) octahedra by sharing vertex O atoms. Charge neutrality is achieved by K(+) ions located in the free void space. Interestingly, photoluminescence studies show that Tb(0.88)Eu(0.12)GeO-JU-87 and Tb(0.67)Eu(0.33)GeO-JU-87 exhibit a high Tb(3+)-to-Eu(3+) energy-transfer efficiency and the Tb(x)Eu(1-x)GeO-JU-87 system displays tunable photoluminescent properties.     

Increasing the structural complexity of chromium(IV) oxides by high-pressure and high-temperature reactions of CrO2

This work presents an overview of a series of increasingly complex oxides synthesized from CrO 2, under high-pressure and high-temperature conditions, having Cr (4+) in octahedral coordination. Although the emphasis is on the structure and microstructure of the compounds as obtained from X-ray diffraction and transmission electron microscopy and diffraction, attention is also given to their interesting electronic and magnetic properties. The study is complemented with an electron energy loss spectroscopic analysis of the different phases. These are the cubic perovskite SrCrO 3, the orthorhombic perovskite CaCrO 3, the solid solution Sr 1-xCa xCrO 3, the Ruddlesden-Popper-type Sr 3Cr 2O 7, the family CrSr 2RECu 2O 8 (RE = rare earth), a compositionally modulated perovskite "PbCrO 3", and the misfit layer oxide SrO 2[CrO 2] 1.85.     

High-nuclearity metal-cyanide clusters: synthesis,magnetic properties,and inclusion behavior of open-cage species incorporating [(tach)M(CN)3] (M = Cr,Fe, Co) complexes

The use of 1,3,5-triaminocyclohexane (tach) as a capping ligand in generating metal-cyanide cage clusters with accessible cavities is demonstrated. The precursor complexes [(tach)M(CN)(3)] (M = Cr, Fe, Co) are synthesized by methods similar to those employed in preparing the analogous 1,4,7-triazacyclononane (tacn) complexes. Along with [(tach)Fe(CN)(3)](1)(-), the latter two species are found to adopt low-spin electron configurations. Assembly reactions between [(tach)M(CN)(3)] (M = Fe, Co) and [M'(H(2)O)(6)](2+) (M' = Ni, Co) in aqueous solution afford the clusters [(tach)(4)(H(2)O)(12)Ni(4)Co(4)(CN)(12)](8+), [(tach)(4)(H(2)O)(12)Co(8)(CN)(12)](8+), and [(tach)(4)(H(2)O)(12)Ni(4)Fe(4)(CN)(12)](8+), each possessing a cubic arrangement of eight metal ions linked through edge-spanning cyanide bridges. This geometry is stabilized by hydrogen-bonding interactions between tach and water ligands through an intervening solvate water molecule or bromide counteranion. The magnetic behavior of the Ni(4)Fe(4) cluster indicates weak ferromagnetic coupling (J = 5.5 cm(-)(1)) between the Ni(II) and Fe(III) centers, leading to an S = 6 ground state. Solutions containing [(tach)Fe(CN)(3)] and a large excess of [Ni(H(2)O)(6)](2+) instead yield a trigonal pyramidal [(tach)(H(2)O)(15)Ni(3)Fe(CN)(3)](6+) cluster, in which even weaker ferromagnetic coupling (J = 1.2 cm(-)(1)) gives rise to an S = (7)/(2) ground state. Paralleling reactions previously performed with [(Me(3)tacn)Cr(CN)(3)], [(tach)Cr(CN)(3)] reacts with [Ni(H(2)O)(6)](2+) in aqueous solution to produce [(tach)(8)Cr(8)Ni(6)(CN)(24)](12+), featuring a structure based on a cube of Cr(III) ions with each face centered by a square planar [Ni(CN)(4)](2)(-) unit. The metal-cyanide cage differs somewhat from that of the analogous Me(3)tacn-ligated cluster, however, in that it is distorted via compression along a body diagonal of the cube. Additionally, the compact tach capping ligands do not hinder access to the sizable interior cavity of the molecule, permitting host-guest chemistry. Mass spectrometry experiments indicate a 1:1 association of the intact cluster with tetrahydrofuran (THF) in aqueous solution, and a crystal structure shows the THF molecule to be suspended in the middle of the cluster cavity. Addition of THF to an aqueous solution containing [(tach)Co(CN)(3)] and [Cu(H(2)O)(6)](2+) templates the formation of a closely related cluster, [(tach)(8)(H(2)O)(6)Cu(6)Co(8)(CN)(24) superset THF](12+), in which paramagnetic Cu(II) ions with square pyramidal coordination are situated on the face-centering sites. Reactions intended to produce the cubic [(tach)(4)(H(2)O)(12)Co(8)(CN)(12)](8+) cluster frequently led to an isomeric two-dimensional framework, [(tach)(H(2)O)(3)Co(2)(CN)(3)](2+), exhibiting mer rather than fac stereochemistry at the [Co(H(2)O)(3)](2+) subunits. Attempts to assemble larger edge-bridged cubic clusters by reacting [(tach)Cr(CN)(3)] with [Ni(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) complexes instead generated extended one- or two-dimensional solids. The magnetic properties of one of these solids, two-dimensional [(tach)(2)(cyclam)(3)Ni(3)Cr(2)(CN)(6)]I(2), suggest metamagnetic behavior, with ferromagnetic intralayer coupling and weak antiferromagnetic interactions between layers.     

Effects of Composition on the Structure and Capacitive Properties of Ti/(ZrO2)x(RuO2)1-x Electrodes

<正>A series of nominal composition Ti/(ZrO_2)_x(RuO_2)_(1-x) (0.1≤x≤0.9) coatings chan- ged in 10% steps was deposited on titanium substrate from RuCl_3·nH_2O and ZrCl_4 containing ethanol solution by thermal decomposition method. The X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM) and electrochemical tests were performed to clarify the effects of ZrO_2 content on the structure and capacitive property of Ti/(ZrO_2)_x(RuO_2)_(1-x). The results show that by adding ZrO_2 into the coatings the degree of crystallization of RuO_2 decreases. The specific capacitance firstly increases and then deceases with the increase of ZrO_2 content in the mixed oxide coatings. The film of Ti/(ZrO_2)_(0.6)(RuO_2)_(0.4) consisting of amorphous matrix and fine nano-crystalline RuO_2 (about 4 nm) has the maximum specific capacitance of 713.27 F/g(RuO_2).     

Increasing the ordering temperatures in oxalate-based 3D chiral magnets: the series [Ir(ppy)2(bpy)][M(II)M(III)(ox)3] x 0.5 H2O (M(II)M(III) = MnCr, FeCr, CoCr, NiCr, ZnCr, MnFe, FeFe); bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine; ox = oxalate dianion)

The synthesis, structure, and physical properties of a novel series of oxalate-based bimetallic magnets obtained by using the Ir(ppy)2(bpy)]+ cation as a template of the bimetallic [M(II)M(III)(ox)3]- network are reported. The compounds can be formulated as [Ir(ppy)2(bpy)][M(II)Cr(III)(ox)3] x 0.5 H2O (M(II) = Ni, Mn, Co, Fe, and Zn) and [Ir(ppy)2(bpy)]-[M(II)Fe(III)(ox)3] x 0.5 H2O (M(II) = Fe, Mn) and crystallize in the chiral cubic space group P4(1)32 or P4(3)32. They show the well-known 3D chiral structure formed by M(II) and M(III) ions connected through oxalate anions with [Ir(ppy)2(bpy)]+ cations and water molecules in the holes left by the oxalate network. The M(II)Cr(III) compounds behave as soft ferromagnets with ordering temperatures up to 13 K, while the Mn(II)Fe(III) and Fe(II)Fe(III) compounds behave as a weak ferromagnet and a ferrimagnet, respectively, with ordering temperatures of 31 and 28 K. These values represent the highest ordering temperatures so far reported in the family of 3D chiral magnets based on bimetallic oxalate complexes.     

Anionic Fischer-type carbene complexes as bidentate (N,O) ligands

New polynuclear complexes, (L1)3M2 [M2 = Cr(III) (4a,4b), Fe(III) (5), Co(III) (8)], (L1)2M2(L2)2 [M2 = Co(II) (7), Ni(II) (9)], (L1)2M2(O)L2 [M2 = V(IV) (6)] and L1M2Cp2 [M2 = Ti(III) (10)] with L1 = (CO)5M1=C[C=NC(CH3)=CHS](O-)(M1 = Cr or W) and L2 = 4-methylthiazole or THF, are described. The molecular structures of these complexes determined by X-ray diffraction show that the Fischer-type carbene complexes act as bidentate ligands towards the second metal centre, coordinating through C(carbene)-attached O-atoms and imine N-atoms of the thiazolyl groups to form five-membered chelates with the oxygen atoms in the mer configuration. Isostructural complexes have similar characteristic band patterns in their far-IR spectra. Cyclic voltammetry of selected complexes reveals the oxidation of the carbene complex ligand between 1.01 and 1.29 V. Oxidation of the central metal (M2) takes place at 0.56 and 0.86 V for 7 and 9, respectively. Three stepwise reductions of Cr(III) to Cr(0) occur for 4a and 4b in the region -0.51 to -1.58 V. These new ligand types and other variants thereof should find application in ligand design with the first metal -- and other ligands attached thereto -- in the carbene complex ligand, playing an important role.