新的富金属三组元层状碲化物TaNi2Te2的合成和晶体结构

通过高温固相反应合成了标题化合物并测定了其晶体结构．结晶学参数：正交晶系，空间群Pnma，Z＝4，α＝0.6480(1)；b＝0.35639(6)，c＝1.6994(4) nm，V＝0.3925(1) nm，D_c＝9.37 g·cm~(-3)，λ(MoK_α)＝0.071069 nm，μ(MoK_α)＝514.43 cm~(－1)，F(000)＝932，最终偏离因子R＝0.051．TaNi_2Te_2是一新的富金属三级元层状碲化物，在结构中两层金属原子夹于碲原子层之间，形成对Ta原子的平面三角形碲配位和对Ni原子的三角锥碲配位．演化合物的一个重要结构特征是平面形的五元环TeNi_4孪合形成扩展结构而每个Ta原子夹于两个TeNi_4五元环之间．     

X‐ray Diffraction and Solid‐State NMR Studies of a Germanium Binuclear Complex

A compound formulated as (C₄H₁₂N₂)[Ge₂(pmida)₂(OH)₂] ? 4 H₂O (where pmida^4?=N‐(phosphonomethyl)iminodiacetate and C₄H₁₂N₂²⁺=piperazinedium cation), containing the anionic [Ge₂(pmida)₂(OH)₂]^2? complex, has been synthesised by the hydrothermal approach and its structure determined by single‐crystal X‐ray diffraction analysis. Several high‐resolution solid‐state magic‐angle spinning (MAS) NMR techniques, in particular two‐dimensional ¹H–X(¹³C,³¹P) heteronuclear correlation (HETCOR) and ¹H–¹H homonuclear correlation (HOMCOR) experiments incorporating a frequency‐switched Lee–Goldburg (FS‐LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic–organic hybrids. We assigned the NMR resonances with the help of C ??? H and P ??? H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X‐ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry).     

Halometallate Complexes of Germanium(II) and (IV): Probing the Role of Cation,Oxidation State and Halide on the Structural and Electrochemical Properties

The Ge^IV chlorometallate complexes, [EMIM]₂[GeCl₆], [EDMIM]₂[GeCl₆] and [PYRR]₂[GeCl₆] (EMIM=1‐ethyl‐3‐methylimidazolium; EDMIM=2,3‐dimethyl‐1‐ethylimidazolium; PYRR=N‐butyl‐N‐methylpyrrolidinium) have been synthesised and fully characterised; the first two also by single‐crystal X‐ray diffraction. The imidazolium chlorometallates exhibited significant C?H???Cl hydrogen bonds, resulting in extended supramolecular assemblies in the solid state. Solution ¹H NMR data also showed cation–anion association. The synthesis and characterisation of Ge^II halometallate salts [EMIM][GeX₃] (X=Cl, Br, I) and [PYRR][GeCl₃], including single‐crystal X‐ray analyses for the homologous series of imidazolium salts, are reported. In these complexes, the intermolecular interactions are much weaker in the solid state and they appear not to be significantly associated in solution. Cyclic‐voltammetry experiments on the Ge^IV species in CH₂Cl₂ solution showed two distinct, irreversible reduction waves attributed to Ge^IV–Ge^II and Ge^II–Ge⁰, whereas the Ge^II species exhibited one irreversible reduction wave. The potential for the Ge^II–Ge⁰ reduction was unaffected by changing the cation, although altering the oxidation state of the precursor from Ge^IV to Ge^II does have an effect; for a given cation, reduction from the [GeCl₃]^? salts occurred at a less cathodic potential. The nature of the halide co‐ligand also has a marked influence on the reduction potential for the Ge^II–Ge⁰ couple, such that the reduction potentials for the [GeX₃]^? salts become significantly less cathodic when the halide (X) is changed Cl→Br→I.     

Group II Metal Complexes of the Germylidendiide Dianion Radical and Germylidenide Anion

The two‐electron reduction of a Group 14‐element(I) complex [RË?] (E=Ge, R=supporting ligand) to form a novel low‐valent dianion radical with the composition [RË:]^{. 2?} is reported. The reaction of [LGeCl] ( 1 , L=2,6‐(CH?NAr)₂C₆H₃, Ar=2,6‐iPr₂C₆H₃) with excess calcium in THF at room temperature afforded the germylidenediide dianion radical complex [LGe]^{. 2?}?Ca(THF)₃²⁺ ( 2 ). The reaction proceeds through the formation of the germanium(I) radical [LGe?], which then undergoes a two‐electron reduction with calcium to form 2 . EPR spectroscopy, X‐ray crystallography, and theoretical studies show that the germanium center in 2 has two lone pairs of electrons and the radical is delocalized over the germanium‐containing heterocycle. In contrast, the magnesium derivative of the germylidendiide dianion radical is unstable and undergoes dimerization with concurrent dearomatization to form the germylidenide anion complex [C₆H₃‐2‐{C(H)?NAr}Ge‐Mg‐6‐{C(H)‐NAr}]₂ ( 3 ).     

Solvothermal Synthesis and Characterization of HgTe Nanoplatelets Using Mercury(Ⅰ) Source

Mercury telluride (HgTe) nanoplatelets were obtained via a facile solvothermal reaction of mercury(Ⅰ) chloride and tellurium powder in ethylenediamine (en). Mercury(Ⅰ) was first applied as the mercury sources to prepare nanocrystal HgTe; moreover, the proposed mechanism for the fabrication of the sample was discussed in detail. The HgTe nanoplatelets were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM),transmission electron microscopy (TEM), high-resolution transmission electron microscopy(HRTEM) and Fourier transform infrared spectroscopy (FT-IR). The absence of IR absorption may render the title nanocrystal useful as an IR transparent material in the region.     

Ge diffusion on Si surfaces

Ge diffusion on Si(100), (111), and (110) surfaces has been studied by Auger electron spectroscopy and low energy electron diffraction in the temperature range from 600 to 800 °C. Surface diffusion coefficients versus temperature have been measured.     

Use of germanium initiators in ring‐opening polymerization of L‐lactide

Three different, new germanium initiators were used for ring‐opening polymerization of L ‐lactide. Chlorobenzene and 120 °C was a usable polymerization system for solution polymerization, and the results from the polymerizations depended on the initiator structure and bulkiness around the insertion site. The average molecular weights as measured by size exclusion chromatography increased linearly with the monomer conversion, and the molecular weight dispersity was around 1.2 for initiators 1 and 2 , whereas it was around 1.4 for initiator 3 . The average molecular weight of poly(L ‐lactide) could be controlled with all three initiators by adding different ratios of monomer and initiator. The reaction rate for the solution polymerization was, however, overall extremely slow. With an initial monomer concentration of 1 M and a monomer‐to‐initiator ratio of 50, the conversion was 93% after 161 h for the fastest initiator. In bulk polymerization, 160 °C, the conversion was 90% after 10 h. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3074–3082, 2003     

IR laser‐induced synthesis of nanostructured gemanium telluride in the gas phase

The gas‐phase synthesis and chemical vapour deposition of nanostructured germanium telluride has been achieved for the first time. The pulsed IR laser irradiation of gaseous CH₃)₄Ge? (CH₃)₂Te? SF₆ mixtures results in homogeneous decomposition of both organometallics and formation of GeTe_x (x = 1, 2). The amorphous GeTe₂ and crystalline GeTe were identified by Raman and X‐ray photoelectron spectroscopy and by electron diffraction. Their formation is explained by an intermediacy of germanium and tellurium clusters and by reaction between these clusters in a hot laser‐induced zone. Copyright © 2005 John Wiley & Sons, Ltd.     

Investigations on the Diffusion of Boron in SiGe Mixed Crystals

By studying the quadrupolar interaction of ¹²B in silicon–germanium mixed crystals with the β-NMR method, the boron–germanium pair was identified and the saturation amplitudes for boron in differently composed crystals were measured. The relative saturation amplitudes agree with statistical predictions. At low temperatures boron is preferentially implanted into stable interstitial sites. These sites are converted into substitutional sites by diffusion processes which take advantage of reorientation jumps.     

单晶锗表面键合光敏染料的研究

本文在烯丙醇单体上进行了两种一甲川菁的合成,并用一种新的化学键合法将两种一甲川菁染料键合在抛光的半导体单晶锗表面。将键合有光敏染料的锗片进行了激光Raman光谱及XPS谱测试,结果表明,与对照锗片相比,键合后的锗片表面,锗衬底的一级拉曼峰强度减少,并在600～3200cm~(-1)范围内出现了与键合颜料分子相应的拉曼频移;在XPS谱中,分别进行了C,N,O,S,卤素等原子的谱图分析,证实了键合颜料后半导体单晶锗表面增加了C—N,S—C,C—O等键,结果与键合的颜料分子结构相符,表明两种光敏染料通过锗氧键共价键合于锗表面。