Übergangsmetallchalkogenverbindungen. Über CuNH4WS4 und Cu2WS4 und andere Übergangsmetallchalkogenmetallate

Transition metal chalkogen compounds. On CuNH₄WS₄, Cu₂WS₄ and other transition metal chalkogenometallates The preparation, vibrational and electronic spectra of CuNH₄WS₄, Cu₂WS₄ and other transition metal compounds, which could not be isolated in a pure form, are reported. The X-ray data of CuNH₄WS₄ are given.     

Synthesis and characterisation of a new high pressure polymorph of Cu2WS4

In this communication we report the synthesis and structural characterisation of a new body centred polymorph of Cu2WS4 prepared using hydrothermal methods. I-Cu2WS4 crystallises in space group I42m with cell parameters a = b = 5.44427(8), c = 10.0687(2) A and has a new structure type containing layers of edge-sharing CuS4 and WS4 tetrahedra.     

WS4Cu3I2]- and [WS4Cu4]2+ secondary building units formed a metal-organic framework: large tubes in a highly interpenetrated system

A 3D metal-organic framework, {[WS(4)Cu(4)(dpbp)(4)](2+)·[WS(4)Cu(3)(dpbp)(2)I(2)](-)·I(-)}(n)·xSolvent, [dpbp = 4,4'-di(4-pyridyl)biphenyl] with an unprecedent 8-fold non-equivalent interpenetration mode is presented, which contains four anionic and four cationic frameworks formed by tetranuclear [WS(4)Cu(3)I(2)](-) and pentanuclear [WS(4)Cu(4)](2+) SBUs with long dpbp ligands. Large rhombus-shaped tubes with diagonal dimensions of ~20 × 10 ? are formed in spite of high interpenetration.     

[WS4Cu2（Py）4]的合成及晶体结构

(NH_4)_2WS_4、CuCl和(n-Bu)_4NBr在Ar气氛中,90℃下反应10 h,所得产物先后经CH_2Cl_2与CH_3OH处理,得一桔红色晶体。该晶体与吡啶反应,即得到桔红色针状晶体[WS_4Cu_2(Py)_4],属单斜晶系,空间群C2/c,晶胞参数:a=14.109(1),b=12.704(1),c=14.071(1);β=96.97(1)°;Z=4。结构用重原子法解出,经最小二乘法修正,偏离因子R=0.027。     

Novel route to WOx nanorods and WS2 nanotubes from WS2 inorganic fullerenes

WO(x) (2 < x < 3) and WS(2) nanostructures have been widely praised due to applications as catalysts, solid lubricants, field emitters, and optical components. Many methods have been developed to fabricate these nanomaterials; however, most attention was focused on the same dimensional transformation from WO(x) nanoparticles or nanorods to WS(2) nanoparticles or nanotubes. In a solid-vapor reaction, by simply controlling the quantity of water vapor and reaction temperature, we have realized the transformation from quasi-zero-dimensional WS(2) nanoparticles to one-dimensional W(18)O(49) nanorods, and subsequent sulfuration reactions have further converted these W(18)O(49) nanorods into WS(2) nanotubes. The reaction temperature, quantity of water vapor, and pretreatment of the WS(2) nanoparticle precursors are important process parameters for long, thin, and homogeneous W(18)O(49) nanorods growth. The morphologies, crystal structures, and circling transformation mechanisms of sulfide-oxide-sulfide are discussed, and the photoluminescence properties of the resulting nanorods are investigated using a Xe lamp under an excitation of 270 nm.     

Shock-wave resistance of WS2 nanotubes

The shock-wave resistance of WS(2) nanotubes has been studied and compared to that of carbon nanotubes. Detailed structural features of post-shock samples were investigated using HRTEM, XRD, and Raman spectroscopy. WS(2) nanotubes are capable of withstanding shear stress caused by shock waves of up to 21 GPa, although some nanotube tips and nanoparticles containing multiple structural defects in the bending regions are destroyed. Small WS(2) species, consisting of only a few layers, are extruded from the nanotubes. Well-crystallized tube bodies were found to exhibit significant stability under shock, indicating high tensile strength. XRD and Raman analyses have confirmed this structural stability. Under similar shock conditions, WS(2) tubes are more stable than carbon nanotubes, the latter being transformed into a diamond phase. WS(2) nanotubes containing small concentrations of defects possess significantly higher mechanical strength, and, as a consequence, hollow WS(2) nanoparticles are expected to act as excellent lubricants under much higher loading than was previously thought.     

Mechanical Properties of WS2 Nanotubes

Their mesoscopic dimensions (including a nanometer scale diameter and a micrometer scale length) make nanotubes a unique and attractive object of study, including the study of their mechanical properties and fracture in particular. The investigation of the mechanical properties of individual WS₂ nanotubes is a challenging task due to their small size. Hence, various microscopy based techniques were used to overcome this challenge. The Young’s modulus was studied by techniques like atomic force microscope (AFM) and scanning electron microscope (SEM); it was also calculated by using the density-functional-based tight-binding (DFTB) method. Tensile tests and bending tests of individual WS₂ nanotubes were performed as well. Furthermore, the shock wave resistance of these nanotubes was tested. The Young’s modulus of WS₂ nanotubes was found to be in the range of 150–170 GPa, which is in good agreement with DFTB calculations. WS₂ nanotubes also showed tensile strength as high as 16 GPa and fracture strain of 14%. These results indicate the high quality of these nanotubes which reach their theoretical strength. The interlayer shear (sliding) modulus was found to be ca. 2 GPa, this value is in good agreement with DFTB calculations. Moreover, the nanotubes were able to withstand shock waves as high as 21 GPa.     

Methane Adsorption on Planar WS2 and on WS2-Fullerene and -Nanotube Containing Samples

Adsorption-desorption cycles were measured for methane on non-irradiated WS₂, and on irradiated WS₂ (which contained, in part, WS₂ fullerenes and nanotubes). Both types of samples were further subdivided into three sets: one set received no further treatment, another set was heated under vacuum, and the last set was acid-treated and heated. The specific surface area was determined for each set; so was the presence or absence of a hysteresis loop in the adsorption-desorption cycles. The results of these two groups of measurements were correlated with the space available for adsorption. The implications of the results for the experimental determination of the dimensionality of gas adsorbed at the interior of nanotubes are discussed.     

Acetic acid induced self-assembly of supramolecular compounds [Et4N]3[(WS4Cu2)2(mu-CN)3].2MeCN and [PPh4][WS4Cu3(mu-CN)2].MeCN from preformed clusters [A]2[WS4(CuCN)2] (A = Et4N, PPh4)

Reactions of two preformed trinuclear W/Cu/S clusters, [A](2)[WS(4)(CuCN)(2)] (1: A = Et(4)N; 2: A = PPh(4)), with different concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et(4)N](3)[(WS(4)Cu(2))(2)(mu-CN)(3)].2MeCN (3), and [PPh(4)][WS(4)Cu(3)(mu-CN)(2)].MeCN (4), respectively. Compound 4 can also be readily obtained in a high yield from the reaction of 2 with equimolar [Cu(MeCN)(4)]PF(6) in MeCN. These compounds have been characterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray analysis reveals that compound 3 retains the WS(4)Cu(2) cluster core, which serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound 4 consists of a T-shaped WS(4)Cu(3) core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or double cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of 3 and 4 from the two cluster precursors 1 and 2 suggests that this simple synthetic strategy is likely to be applicable to many related systems.     

Solid state synthesis of copper(I) thiotungstate cluster compounds at low heating temperatures. Crystal structures of [(n-Bu)4N]3-[WS4Cu3Cl3Br] and [Et4N]4[WS4Cu4I6]

Summary Reaction of [NH₄]₂[WS₄] with CuX (X = Cl or I) and R₄NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)₄N]₃[WS₄Cu₃Cl₃Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Å, V = 9661.8 ų, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS₃Cu₃Br] of C₃ symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et₄N]₄[WS₄Cu₄I₆], crystallizes in the monoclinic space group C2/m with a = 29.702(6), b = 12.7887(5), c = 15.327(3)Å, = 99.69(2), V = 5738.1 ų, Z = 4. In the cluster anion of (2), four edges of the WS₄ core are coordinated by four Cu atoms, giving a WS₄Cu₄ aggregate of approximate C_2V symmetry.     

Excited state absorption dynamics in metal cluster polymer [WS4Cu3I(4-bpy)3]n solution

The nonlinear absorptive property of a novel metal cluster [WS(4)Cu(3)I(4-bpy)3]n in DMF solution is studied by using an open-aperture Z-scan technique with picosecond and nanosecond laser pulses at the wavelength of 532 nm. The experimental results show that the cluster has strong nonlinear absorption under the 8 ns pulse excitation and a relatively weak nonlinear absorptive property under the picosecond pulse excitation. The picosecond pump-probe response of the metal cluster is similar to that of C60 solution, which implies that the nonlinear mechanisms are the same for the two materials. By using the rate-equation model, the experimental data are theoretically simulated; several optical parameters of the cluster, especially the lifetime of the higher excited singlet state of the cluster, are obtained.     

Metal-organic frameworks constructed from versatile [WS4Cu(x)](x-2) units: micropores in highly interpenetrated systems

Five metal-organic frameworks (MOFs) formed by [WS(4)Cu(x)](x-2) secondary building units (SBUs) and multi-pyridyl ligands are presented. The [WS(4)Cu(x)](x-2) SBUs function as network vertexes showing various geometries and connectivities. Compound 1 contains one-dimensional channels formed in fourfold interpenetrating diamondoid networks with a hexanuclear [WS(4)Cu(5)](3+) unit as SBU, which shows square-pyramidal geometry and acts as a tetrahedral node. Compound 2 contains brick-wall-like layer also with a hexanuclear [WS(4)Cu(5)](3+) unit as SBU. The [WS(4)Cu(5)](3+) unit in 2 is a new type of [WS(4)Cu(x)](x-2) cluster unit in which the five Cu(+) ions are in one plane with the W atom, forming a planar unit. Compound 3 shows a nanotubular structure with a pentanuclear [WS(4)Cu(4)](2+) unit as SBU, which is saddle-shaped and acts as a tetrahedral node. Compound 4 contains large cages formed between two interpenetrated (10,3)-a networks also with a pentanuclear [WS(4)Cu(4)](2+) unit acting as a triangular node. The [WS(4)Cu(4)](2+) unit in 4 is isomeric to that in 3 and first observed in a MOF. Compound 5 contains zigzag chains with a tetrahedral [WS(4)Cu(3)](+) unit as SBU, which acts as a V-shaped connector. The influence of synthesis conditions including temperature, ligand, anions of Cu(I) salts, and the ratio of [NH(4)](2)WS(4) to Cu(I) salt on the formation of these [WS(4)Cu(x)](x-2)-based MOFs were also studied. Porous MOF 3 is stable upon removal and exchange of the solvent guests, and when accommodating different solvent molecules, it exhibits specific colors depending on the polarity of incorporated solvent, that is, it shows a rare solvatochromic effect and has interesting prospects in sensing applications.     

Formation and Stability of Gaseous WS2Cl2, WS2Br2 and WS2I2 – A Combined Experimental and Theoretical Study

Gaseous WS₂Cl₂ and WS₂Br₂ are formed by the reaction of solid WS₂ with chlorine resp. bromine at temperatures of about 1000 K. This could be shown by mass spectrometric measurements. The heats of formation and entropies of WS₂Cl₂ and WS₂Br₂ have been determined by means of mass spectrometry (MS) and quantum chemical calculations (QC). WS₂I₂ could not be detected by experimental methods. This is in line with the quantum chemically determined equilibrium constant of the formation reaction. The following values are given:, Δ_fH⁰₂₉₈(WS₂Cl₂) = –230.8 kJ · mol^–1 (MS), Δ_fH⁰₂₉₈(WS₂Cl₂) = –235.0 kJ · mol^–1 (QC),, S⁰₂₉₈(WS₂Cl₂) = 370.7 J · K^–1 · mol^–1 (QC) and, c_p⁰_T(WS₂Cl₂) = 103.78 + 7.07 × 10^–3 T – 0.93 × 10⁵ T^–2 – 3.25 × 10^–6 T² (298.15 K < T < 1000 K) (QC). Δ_fH⁰₂₉₈(WS₂Br₂) = –141.9 kJ · mol^–1 (MS), Δ_fH⁰₂₉₈(WS₂Br₂) = –131.5 kJ · mol^–1 (QC),, S⁰₂₉₈(WS₂Br₂) = 393.9 J · K^–1 · mol^–1 (QC) and, c_p⁰_T(WS₂Br₂) = 104.84 + 5.32 × 10^–3 T – 0.75 × 10⁵ T^–2 – 2.45 × 10^–6 T² (298.15 K < T < 1000 K) (QC). Δ_fH⁰₂₉₈(WS₂I₂) = –18.0 kJ · mol^–1 (QC), S⁰₂₉₈(WS₂I₂) = 409.9 J · K^–1 · mol^–1 (QC) and, c_p⁰_T(WS₂I₂) = 105.17 + 4.77 × 10^–3 T – 0.67 × 10⁵ T^–2 – 2.19 × 10^–6 T² (298.15 K < T < 1000 K) (QC). These molecules have the expected C_2v‐symmetry.