Some new members of MAX family including light-elements: Nanolayered Hf2XY (X= Al,Si, P and Y=B,C, N)

The structural, electronic, mechanical and dynamical properties of new members of MAX family (Hf₂XY, X=Al, Si, P and Y= B, C, N compounds) with Cr₂AlC-type structure have been investigated by first-principles density functional plane-wave pseudopotential calculations within generalized gradient approximation. From calculated cohesive energies, all compounds are energetically stable. And, from calculated elastic constants and phonon dispersion curves, it is shown that all compounds are mechanically stable, while the boron including ones are dynamically unstable except for Hf₂PB. At the same time, related mechanical properties such as bulk and shear moduli are calculated. For further mechanical characterization, hardnesses of the compounds are determined theoretically. It is observed from electronic structure calculations including band structure and partial density of states, all stable compounds are metallic. Additionally, bonding nature of the compounds are analyzed by using 3D and 2D electron density maps, Mulliken atomic charges and bond overlap populations.     

Microstructure,Mechanical and Electrical Properties of Hybrid Copper Matrix Composites with Fe Microspheres and rGO Nanosheets

Copper matrix composites have a wide application as magnetic conductive materials, electromagnetic materials, electrical discharge machining materials, etc. Such materials are expected to have a good combination of excellent electrical conductivity and good mechanical strength. In this work, micro/nano hybrid reinforcements with Fe microspheres and reduced graphene oxide (rGO) nanosheets were developed for copper matrix composites. The rGO/Fe/Cu powders were firstly wet-mixed and then densified by the vacuum hot-pressing sintering to obtain the bulk compacts. Microstructure, electrical conductivity and mechanical properties of such compacts were investigated. Microstructural result of as-sintered compacts shows that the Fe microspheres could distribute in the matrix uniformly, and rGO nanosheets exhibit both agglomerated and dispersed states. The grain size of Cu matrix decreased with the increase of the rGO content. Hardness, compression and tensile 0.2% yield strength of the as-sintered compacts were improved evidently by the addition of the hybrid Fe/rGO, comparing with pure Cu and single Fe-added composites. However, a lower electrical conductivity appeared in the more rGO-added composites, but still reached more than 33.0% international annealing copper standard (IACS). These performance change could be sought in the spatially geometrical distribution and characteristics of such micro/nano Fe/rGO hybrid addition, and the relevant mechanisms were discussed.     

Aurivillius Phases in the Bi4Ti3O12/BiFeO3 System: Thermal Behaviour and Crystal Structure

Four compounds of the Bi₄Ti₃O₁₂/BiFeO₃ system with the formula Bi₂Bi_n?1(Ti,Fe)_nO_3n+3, n = 3, 4, 4.5 and 6 were studied using high‐temperature X‐ray powder diffraction and differential thermoanalysis methods. The crystal structure of the n = 6 phase was refined by the Rietveld method. An unusual behaviour of thermal expansion attributed to an orthorhombic‐to‐tetragonal transformation was revealed. For all the compounds, the lattice parameter c vs temperature T dependence has three regions in the range of T = 20 –750 °C interpreted as (1) expansion of the initial orthorhombic phase, (2) a pronounced structure reconstruction to the tetragonal phase, (3) an expansion of the tetragonal phase. The crystal structure of Bi₇Ti₃Fe₃O₂₁ based on 6‐layer‐perovskite blocks is proposed from X‐ray powder diffraction data. The Rietveld refinement of the structure in the orthorhombic space group F2mm with lattice parameters a = 5.4699(3), b = 5.4924(3), c = 57.551(3) Å (R_p = 9.4, R_wp = 11.9, R_exp = 4.7, R_B = 4.4 %) shows that a distorted 6‐layer model fits the data of Bi₇Ti₃Fe₃O₂₁.     

La0.75Sr0.25Cr0.5Mn0.5O3的制备及其NO2气敏性能

利用高温固相反应法和溶胶-凝胶法制备了La0.75Sr0.25Cr0.5Mn0.5O3钙钛矿复合氧化物粉体。采用XRD,TEM对粉体物相组成及颗粒形貌进行表征,并以制备的两种粉体作为敏感材料分别制成管状传感器,测试了其NO2气敏性能。结果表明：采用高温固相反应法和溶胶-凝胶法在不同焙烧温度下,均可制得单相La0.75Sr0.25Cr0.5Mn0.5O3粉体,采用溶胶-凝胶法在800℃焙烧2 h得到的粉体粒径约为20 nm;传感器输出电动势信号对NO2浓度之间呈良好的线性关系;溶胶-凝胶法制得粉体的气敏性能优于高温固相反应法制得粉体的气敏性能。     

Fabrication of Single Wall Carbon Nanotubes-Based Poly(vinyl butyral) Nanocomposites with Enhanced Mechanical and Thermal Properties

In this research, poly(vinyl butyral) (PVB)/single wall carbon nanotubes (SWCNT) composites were prepared via solution blending method. Dispersion degree of SWCNT in the composites was characterized by Scanning Electron Microscopy (SEM) and mechanical properties were measured with tensile testing. Thermal degradation of composites was investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). SEM analysis confirmed good dispersion of the nanotubes in the PVB. The tensile tests showed significant increases in mechanical properties such as exceptional improvement in tensile strength, Young's modulus and flexibility for the composites compared to PVB at low SWCNT content.The TGA curves indicated that adding SWCNT improved the thermal stability of the PVB significantly and the degradation of the polymer matrix shifted to the higher temperatures. For the sample containing 0.6 wt%, an increase of 171% in modulus and a 258.4% enhancement of tensile strength were achieved. Also, elongation at break increased 28.7% at this loading. In fact, intrinsic properties of nanotubes caused enhancement of strength and flexibility simultaneously. Also, for this composite, T_onset and T_max enhanced remarkably and weight loss reduced greatly and residue at 600°C increased to high values. These results are promising for application of the PVB in industry.     

Structure,Optical, and Magnetic Properties of (PPN+)2(C702−)⋅2 C6H4Cl2, which Contains Dianionic Polymeric (C702−)n Chains

A new salt, (PPN⁺)₂(C₇₀^2?) ? 2 C₆H₄Cl₂ ( 1 ), which contains C₇₀^2? dianions, has been obtained as single crystals (PPN⁺=bis(triphenylphosphine)iminium cation). The C₇₀^2? dianions form polymeric zigzag (C₇₀^2?)_n chains, in which the fullerene units are bonded through single C? C bonds of length 1.581(5)–1.586(6) Å. The distance between the centers of neighboring C₇₀^2? units is 10.441 Å. The optical and magnetic properties of (C₇₀^2?)_n have also been studied. Decreasing the symmetry of C₇₀ in the polymer activate about 20 new IR bands in addition to the 10 IR‐active bands of the starting C₇₀. The polymeric structure shows absorptions in the visible and NIR regions, with three main bands at 890, 1200, and 1550 nm, instead of one band of isolated C₇₀^2? dianions at 1165–1184 nm. We concluded that the (C₇₀^2?)_n polymer was diamagnetic, with a negative molar magnetic susceptibility of ?3.82×10^?4 emu mol^?1 per C₇₀^2? dianion. The polymer is EPR silent and a weak narrow EPR signal in salt 1 is due to impurities, which only constitute 0.84 % of spin S=1/2 of the total amount of fullerene C₇₀.     

Beyond the structure-property relationship paradigm: influence of the crystal structure and microstructure on the Li+ conductivity of La2/3Li(x)Ti(1-x)Al(x)O3 Oxides

The crystal structures of several oxides of the La(2/3)Li(x)Ti(1-x)Al(x)O(3) system have been studied by selected-area electron diffraction, high-resolution transmission electron microscopy, and powder neutron diffraction, and their lithium conductivity has been by complex impedance spectroscopy. The compounds have a perovskite-related structure with a unit cell radical2 a(p)x2 a(p)x radical2 a(p) (a(p)=perovskite lattice parameter) due to the tilting of the (Ti/Al)O(6) octahedra and the ordering of lanthanum and lithium ions and vacancies along the 2 a(p) axis. The Li(+) ions present a distorted square-planar coordination and are located in interstitial positions of the structure, which could explain the very high ionic conductivity of this type of material. The lithium conductivity depends on the oxide composition and its crystal microstructure, which varies with the thermal treatment of the sample. The microstructure of these titanates is complex due to formation of domains of ordering and other defects such as strains and compositional fluctuations.     

ChemInform Abstract: Structural,Electronic and Elastic Properties of MAX Phases M2GaN (M: Ti,V and Cr)

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Unusual coexistence of magnetic and nonmagnetic Mo6 octahedral clusters in a chalcohalide solid solution: synthesis, X-ray diffraction, EPR, and DFT investigations of Cs3Mo6Ii6Ii2-xSeixIa6

The Cs3Mo6Ii6Ii2-xSeixIa6 series has been obtained by a solid-state route. There is evidence for a solid solution between the compositions Cs3Mo6Ii6Ii0.8Sei1.2Ia6 and Cs3Mo6Ii6Ii0.4Sei1.6Ia6 (space group: R3c, Z=6; a=16.7065(4), c=20.5523(4) A, V=4967.8(2) A3 and a=16.6354(3), c=20.5444(4) A, V=4923.7(2) A3, respectively). The structure of this new series is based on magnetic [Mo6Ii6Sei2Ia6]3- and diamagnetic [Mo6Ii7SeiIa6]3- units with 23 and 24 valence electrons per Mo6 cluster, respectively. For a particular x, the structure of Cs3Mo6Ii6Ii2-xSexIa6 is based on a mixture of (x-1) [Mo6Ii6Sei2Ia6]3- with (2-x) [Mo6Ii7SeiIa6]3-. This leads to an average [Mo6Ii6Ii2-xSexIa6]3- ionic unit deduced from single-crystal X-ray diffraction investigations. The two inner positions of the average face-capped [Mo6Ii8-xSeixIa6]3- ionic units (located on the threefold axis of the unit) are randomly occupied by iodine and selenium, whereas the other ligand positions are fully occupied by iodine. Low-temperature electron paramagnetic resonance (EPR) studies reveal a signal split into two components with g||>gperpendicular. The reciprocal double integration intensity of the EPR signal versus T graph reveals a typical Curie law behavior. A density functional theory (DFT) study indicates that occupation of the inner position on the threefold axis by selenium atoms is preferred energetically among the three possible distributions of selenium atoms. The comparison of experimental and theoretical g values confirms the crystallographic analysis and agrees with the axial elongation of the Mo6 cluster within the crystal structure.     

A three-component reaction for diversity-oriented synthesis of polysubstituted piperidines: solution and solid-phase optimization of the first tandem aza[4+2]/allylboration

This article describes the design and optimization of a simple three-component aza[4+2]/allylboration reaction to access polysubstituted alpha-hydroxyalkyl piperidines in a highly diastereocontrolled fashion from maleimides, 4-boronohydrazonodienes, and aldehydes. The aldehyde component does not interfere with the first aza[4+2] step, and it was found that this tandem reaction provides better yields of piperidine products 5 when carried out in one-pot. The required 4-borono-hydrazonodienes 1 are synthesized efficiently from the condensation of 3-boronoacrolein pinacol ester (4) with hydrazines. Overall, the three-component process using N-substituted maleimides as dienophiles produces four stereogenic centers and is quite general. It tolerates the use of a wide variety of aldehydes and hydrazine precursors with different electronic and steric characteristics. By allowing such a wide substrate scope and up to four elements of diversity, this reaction process is particularly well adapted towards applications in diversity-oriented synthesis of polysubstituted piperidine derivatives. The suitability of the aza[4+2]/allylboration reaction for use in solid-phase chemistry was also demonstrated using a N-arylmaleidobenzoic acid functionalized resin. This novel multicomponent reaction thus offers a high level of stereocontrol and versatility in the preparation of densely functionalized nitrogen heterocycles.     

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed.     

Formation of 1 D and 3 D coordination polymers in the solid state induced by mechanochemical and annealing treatments: bis(3-cyano-pentane-2,4-dionato) metal complexes

Bis(3-cyano-pentane-2,4-dionato) (CNacac) metal complex, [M(CNacac)(2)], which acts as both a metal-ion-like and a ligand-like building unit, forms supramolecular structures by self-assembly. Co-grinding of the metal acetates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with CNacacH formed a CNacac complex in all cases: mononuclear complex was formed in the cases of Mn(II), Cu(II) and Zn(II), whereas polymeric ones were formed in the cases of Fe(II), Co(II) and Ni(II). Subsequent annealing converted the mononuclear complexes of Mn(II), Cu(II) and Zn(II) to their corresponding polymers as a result of dehydration of the mononuclear complexes. The resultant Mn(II), Fe(II), Co(II), Ni(II) and Zn(II) polymeric complexes had a common 3 D structure with high thermal stability. In the case of Cu(II), a 1 D polymer was obtained. The Mn(II), Cu(II) and Zn(II) polymeric complexes returned to their original mononuclear complexes on exposure to water vapour but they reverted to the polymeric complexes by re-annealing. Co-grinding of metal chlorides with CNacacH and annealing of the mononuclear CNacac complexes prepared from solution reactions were also examined for comparison. [Mn(CNacac)(2)(H(2)O)(2)], [M(CNacac)(2)(H(2)O)] (M=Cu(II) and Zn(II)) and [M(CNacac)(2)](infinity) (M=Mn(II), Fe(II) and Zn(II)) are new compounds, which clearly indicated the power of the combined mechanochemical/annealing method for the synthesis of varied metal coordination complexes.     

ChemInform Abstract: First‐Principles Calculations of the Elastic and Electronic Properties of the Cubic Perovskites SrMO3 (M: Ti,V, Zr and Nb) in Comparison with SrSnO3.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Library‐directed Solution‐ and Solid‐phase Synthesis of 2,4‐Disubstituted Pyridines: One‐pot Approach through 6 π‐Azaelectrocyclization

An efficient one‐pot synthetic procedure for the synthesis of 2,4‐disubstituted pyridines has been successfully established. The method proceeds through a 6π‐azaelectrocyclization‐aromatization sequence. Using this method, a wide variety of pyridine structures substituted at the 2‐position have been rapidly constructed from vinyl stannanes, vinyl iodide, sulfonamide, and a palladium catalyst. The method was further applied to the solid‐phase synthesis wherein the use of a “traceless” sulfonamide linker enabled the rapid preparation of a small library of pyridines with high purity, without any chromatographic separation.