Classifying crystal structures

Common usage has now defined a system for naming crystal structure types of intermetallic phases—but we still need a few arbitrary rules.     

Synthesis, crystal structure and properties of two ternary rare earth complexes with aromatic acid and 1,10-phenanthroline

Two dimeric rare-earth complexes [Eu(o-MOBA)₃phen]₂·2H₂O (1), [Tb(o-MOBA)₃phen]₂·2H₂O (2), (where o-MOBA = o-methoxybenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. Both of them consist of neutral dimeric molecules, crystallize in triclinic system, space group P. Each RE(III) ion is nine-coordinated with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate group, two bidentate bridging carboxylate groups and two tridentate bridging carboxylate groups. Complex 1 shows bright red luminescence, 2 shows green luminescence under UV light at room temperature, respectively. The thermal analysis indicates that they are all quite stable to heat.     

Identifying close-packed planes in complex crystal structures

It is often necessary to identify close-packed or nearly close-packed planes in a crystal. This can be done by inspection in crystal structures where one atom occupies each lattice point – i.e. face-centred cubic and body-centred cubic crystals. However, in more complex crystal structures intuitive inspection becomes rather difficult. The present paper describes a simple method for identifying close-packed or nearly close-packed planes in crystals containing more than one atom per lattice point. The method also distinguishes between “flat” planes, where all the atom centres lie in the plane, and “rumpled” planes, where the atom centres do not lie in the plane. The extent of the departure from true “flatness” can also be estimated.     

High-pressure synthesis and crystal structures of two new polyphosphides, NaP5 and CeP5

Two novel polyphosphides, NaP₅ and CeP₅, were prepared in a BN crucible by the reaction of elemental components under a high pressure of 3 GPa at 800–950 °C. The X-ray structural analysis showed that NaP₅ crystallizes in an orthorhombic space group Pnma with a=10.993(2) Å, b=6.524(1) Å, c=6.903(1) Å, Z=4 and CeP₅ in the monoclinic group P2₁/m with a=4.9143(5) Å, b=9.6226(8) Å, c=5.5152(4) Å, β=104.303(6)°, Z=2. The crystal structure of NaP₅ consists of a three-dimensional framework _∞³[P₅]¹⁻ constructed by P---P bonds among four crystallographically inequivalent phosphorus sites, with large channels hosting the sodium cations, while CeP₅ is a layered compound containing _∞²[P₅]³⁻ polyanionic layers that are separated by Ce³⁺ ions. NaP₅ exhibits the diamagnetic behavior, while the temperature-dependent magnetic susceptibility of CeP₅ essentially follows the Curie–Weiss law.     

Modeling fluid flow in three-dimensional single crystal dendritic structures

Convection during directional solidification can cause defects such as freckles and misoriented grains. To gain a better understanding of conditions associated with the onset of convective instabilities, flow was investigated using three-dimensional (3D) computational fluid dynamics simulations in an experimentally obtained dendritic network. A serial-sectioned, 3D data set of directionally solidified nickel-base superalloy measuring 2.3 × 2.3 × 1.5 mm was used to determine the permeability for flow parallel and normal to the solidification direction as a function of solid fraction (f_S). Anisotropy of permeability varies significantly from 0.4 < f_S < 0.6. High flow velocity channels exhibit spacings commensurate with primary dendrite arms at the base of the mushy zone but rapidly increase by a factor of three to four towards dendrite tips. Permeability is strongly dependent on interfacial surface area, which reaches a maximum at f_S = 0.65. Results from the 3D simulation are also compared with empirical permeability models, and the microstructural origins of departures from these models are discussed.     

Diamine ligands with multiple coplanar conjugation rings and their phosphorescent copper complexes: Synthesis,characterization, crystal structures,and photophysical property

In this paper, we report a series of diamine ligands with multiple coplanar conjugation rings and their corresponding phosphorescent Cu(I) complexes, including their synthesis, crystal structures, photophysical properties, and electronic nature. Geometric parameters suggest that the Cu(I) center localizes at a distorted tetrahedral geometry within the Cu(I) complexes. Theoretical calculation reveals that all emissions originate from triplet metal-to-ligand-charge-transfer excited state. It is found that the free rotation of conjugation rings may compromise the coplanar plane and thus has little effect on the photophysical property of their corresponding Cu(I) complexes. But excess coplanar conjugation moiety is harmful for emissive state. The detailed quenching mechanism is investigated.     

Synthesis of polythienylenevinylene copolymers bearing carbondithioate structures

A new type of thiophene-based copolymers bearing the carbondithioate groups were synthesized through Wittig–Horner reaction. Copolymers were characterized by elemental analysis, UV–Vis, and FT-IR. Conductivity of I₂ doped copolymers ranges from 10⁻³ to 10⁻² S/cm.     

电子束照射下纳米TiO2晶型转变的高分辨透射电镜原位观察

使用场发射透射电镜及其扫描透射装置(STEM)和高角环形暗场像(HAADF)装置及EDS能谱仪研究了溶胶凝胶法制备的TiO2纳米微粒在电子束照射下晶体结构发生变化的现象,在200kV电子束照射下,经过不同时间的原位观察发现,纳米TiO2颗粒由开始的体心正方141/amd(141)锐钛矿TiO2晶型转变为非晶体,随后又在电子束的照射下晶化为简单正方P42/mnm(136)金红石TiO2单晶,随后转变为尺寸更小的金红石TiO2纳米多晶体.HADDF图可以看到最后的晶粒细化过程中,原子有选择的进行迁移,使晶化区域的样品厚度不均匀化,能谱分析证明样品中只有TiO2存在.     

Two Cd(II) coordination polymers based on asymmetrical Schiff-base ligand with five- and six-membered N-containing heterocyclic rings: Synthesis,crystal structures and luminescent properties

Two cadmium inorganic–organic hybrid coordination polymers [CdL(SCN)₂]_n (1) and [CdLI₂]_n (2), have been synthesized and characterized by IR spectroscopy, elemental analysis, XRPD, thermogravimetric (TG) analyses and X-ray crystallography, where L is 4-(pyridine-4-yl)methyleneamino-1,2,4-triazole. Asymmetrical Schiff-base ligand L acts as a bidentate bridging ligand to bind two Cd(II) centers through two terminal N_triazolyl and N_pyridyl donors in polymers 1 and 2. Polymer 1 displays a new 3D inorganic–organic hybrid network generated through the coordination interactions between Cd-(1,3-μ-SCN⁻) 2D inorganic sheets and bidentate bridging ligands. The structure of polymer 2 is a 3D chiral supramolecular framework which contains helical chains on 2₁ axis. Each Cd(II) center is coordinated by two ligands and two I⁻ donors to attain a distorted tetrahedral environment. The luminescent properties of polymers 1 and 2 were investigated in the solid state at room temperature.     

Phase field crystal simulations of nanocrystalline grain growth in two dimensions

We study two-dimensional grain growth at the nanoscale using the phase field crystal (PFC) model. Our results show that for circular grains with large misorientations the grain area decreases linearly with time, in good agreement with classical grain growth theory. For circular grains with small initial misorientations, grain rotation occurs as a result of the coupled motion between the normal motion of the grain boundary and the tangential motion of the adjacent grains. Despite this rotation and its effect on the grain boundary energy, the grain area decreases linearly with time. In addition, for intermediate initial grain misorientations, we find a repeating faceting-defaceting transition during grain shrinkage and a different relationship between the grain area and time, which suggests a different grain growth mechanism than that for small and large misorientations. For a circular grain embedded between a bicrystal with a symmetric tilt boundary, we find that the evolution of the embedded grain closely depends on dislocation reactions at triple junctions.     

两种层状镁硅酸盐矿物的晶体结构与可浮性研究

通过对两种层状镁硅酸盐矿物—蛇纹石和滑石的浮选实验及润湿接触角的测定,研究了蛇纹石与滑石的晶体结构与表面润湿性、可浮性的关系,结果表明:蛇纹石的润湿性较好,可浮性差;滑石的润湿性较差,可浮性好。     

Synthesis and photovoltaic properties of two new unsymmetrical zinc-phthalocyanine dyes

Two new soluble unsymmetrical zinc-phthalocyanine derivatives (PC-HY1, PC-HY2) with D-π-A structure bearing three tert-butylphenyl or tert-butylthienyl groups and cyanoacrylic acid groups were synthesized through a low-cost “anhydride” method. The photophysical, electrochemical and photovoltaic properties of the phthalocyanine derivatives were studied. The two phthalocyanine derivatives showed strong and broad absorption in the UV and red/near-infrared (IR) region, especially for PC-HY2. The electrochemical properties indicated that the two phthalocyanine derivatives are latent materials for dye-sensitized solar cells. Under the illumination of AM 1.5, 100 mW cm⁻², dye-sensitized solar cells based on PC-HY1 and PC-HY2 showed power conversion efficiency (PCE) of 0.79% and 1.09%, respectively.     

Equilibria and kinetics of mass transport between crystal facets: a comparison of two models

The principle of detailed balance is used to evaluate equilibrium between a crystal facet and a transport medium, and transition state theory is then used to evaluate the kinetics of transport between two facets of a particle of nonequilibrium shape. For each of two test geometries undergoing volume-conserved shape changes, the transition state model predicts the same trajectories for detachment/attachment-limited transport as does a continuum model based on the crystalline formulation (Carter et al., Acta metall. mater., 1995, 43, 4309). Both models agree that reported rates of decay of {100} steps in LiF surfaces are not limited by diffusion, and transition state theory shows that detachment is rate limiting. The geometry of the LiF study is like that of particle compacts in that facet edges provide sites for nucleation of monolayer ledges at which attachment or detachment can occur; the two models should both be useful in interpreting sintering studies.     

Synthesis, crystal structures, and optical properties of NaCdPnS3 (Pn = As, Sb)

Two compounds NaCdPnS₃ (Pn = As (1), Sb (2)) were synthesized as transparent yellow and red platelets by reacting cadmium powder with the molten mixtures of Na₂S/As₂S₃/S and Na₂S/Sb/S at 500 °C. Both compounds are plagued with crystal twinning and acceptable crystal structure refinement could only be obtained by identifying the type of the twinning laws. NaCdAsS₃ (1) crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 5.6561(8), b = 16.5487(15), c = 5.6954(8) Å, β = 90.315(11)°, and Z = 4. NaCdSbS₃ (2) crystallizes in the monoclinic space group C2/c (no. 15) with a = 8.1329(6), b = 8.1296(4), c = 17.2600(13) Å, β = 103.499(6)°, and Z = 8. The structures of both compounds feature a ²_∞[CdPnS₃]⁻ layer composed of [CdS₄] tetrahedra and [AsS₃] or [SbS₃] pyramidal units. Between the ²_∞[CdPnS₃]⁻ (Pn = As, Sb) layers the Na⁺ cations reside in a distorted octahedral environment of S atoms. Compound 1 is characterized with UV/Vis diffuse reflectance spectroscopy and IR and Raman spectra.     

Synthesis and crystal structure and nonlinear optical properties of polymeric W （Mo）-Cu-S cluster

The polymeric chalcogenide [W2O2S6Cu4（NCMe）4]n （compound 1） was synthesized by the self-assembly reaction of （NHa）2（WOS3） with CuBr in MeCN in the presence of tricyclohexylphosphane （PCy3） under a purified nitrogen atmosphere using standard Schlenk techniques. It gives rise to a novel ID polymeric compound 1 with solvent MeCN coordinated to the copper atom. This situation is unprecedented in the W（Mo）/Cu/S system. The crystals were characterized by elemental analysis, IR and single-crystal X-ray crystallography. The configuration of the polymeric compound can be viewed as a helical chain which is propagated along the crystallographic c axis. The excited state absorption and refraction of compound 1 in CH3CN solution were studied by using the Z-scan technique with laser pulses of 40 ps pulse-width at a wavelength of 532 nm. The polymeric compound possesses an optical self-focusing performance. The positive nonlinear refraction is attributed to population transitions between singlet states. Compound 1 displays a strong excited-state absorption.     

Synthesis and crystal structure of CaAgBi and BaAg1.837Bi2

Two ternary alkali earth silver bismuthides, CaAgBi and BaAg_1.837Bi₂, have been synthesized by solid-state reactions of the corresponding metals in welded Nb tubes at high temperature. Their structures have been established by single-crystal X-ray diffraction studies. CaAgBi crystallizes in the hexagonal space group P6₃mc (No.186) with cell parameters of a = b = 4.8113(4) Å, c = 7.8273(9) Å, V = 156.92(3) Å³, and Z = 2. BaAg_1.837Bi₂ belongs to tetragonal space group P4/nmm (No.129) with cell parameters of a = b = 4.9202(2) Å, c = 11.628(1) Å, V = 281.50(3) Å³, and Z = 2. The structure of CaAgBi is of the LiGaGe type, and features a three-dimensional four-connected (3D4C) anionic network with Ca²⁺ encapsulated in the channels formed by [Ag₃Bi₃] six-membered rings. BaAg_1.837Bi₂ is isostructural with CaBe₂Ge₂, a variant of the tetragonal ThCr₂Si₂-type structure. Its structure exhibits a three-dimensional anionic network built of (0 0 1) and (0 0 2) puckered [Ag₂Bi₂] layers interconnected via additional Ag–Bi bonds along the c-axis. BaAg_1.837Bi₂ is metallic based on band structure calculations.     

Synthesis,crystal structure and two-photon absorption of a cadmium complex constructed by DMIT ligand

The cadmium complex [(CH₃)₄N][Cd(C₃S₅)₂]·H₂O constructed by 1,3-dithiole-2-thione-4,5-dithiolato (DMIT) ligand has been synthesized and its structure has been determined by means of X-ray single crystal diffraction. Its two-photon absorption (TPA) has been studied in acetonitrile solution using open-aperture Z-scan technique with 20 picosecond (ps) pulses at wavelength 1064 nm. Its TPA coefficient β was determined to be 4.475 × 10^?10 m/W, corresponding the TPA cross-section σ₂ is 3.95 × 10^?53 (m⁴ s/photon molecule).