An EXAFS study of the molecular structure of heterometallic chalcogenide clusters

Applicability of EXAFS spectroscopy for determination of the molecular structure of heterometallic chalcogenide clusters in the crystalline state and in solution was examined. The spatial structure of the metal core of the FeMoW(μ₃-Se)(CO)₇(η⁵-C₅H₅) cluster was determined using EXAFS data obtained at the K absorption edge for Fe, Mo, and Se and at the L_III-edge for W. The geometric parameters (the bond lengths and bond angles) obtained from EXAFS data are close to those determined by X-ray analysis. The Mo K-edge EXAFS study of the structurally similar FeMo₂Te(CO)₇(η⁵-C₅H₅) cluster both in the crystalline state and ino-xylene solution confirmed that the geometry of the metal core of the cluster is retained in solution. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1395–1398, August, 2000.     

Synthesis and structure of supramolecular polyoxothiometalate nanocluster containing 52 metal atoms [{Mo3S4(H2O)5}4(γ-SiW10O36)4]16–

The polyoxothiometalate complex [{Mo₃S₄(H₂O)₅}₄(-SiW₁₀O₃₆)₄]^16– was prepared by the reaction of the cationic triangular molybdenum aqua complex [Mo₃S₄(H₂O)₉]⁴⁺ (electrophile) with the lacunary polyoxotungstate complex [-SiW₁₀O₃₆]^8– (nucleophile). According to the results of single-crystal X-ray diffraction analysis of the dimethylammonium salt, the anionic nanocluster contains 52 molybdenum and tungsten atoms and has a cyclic porphyrin-like structure.     

Mesoporous cadmium sulfide nanoparticles derived from a new cadmium anthranilato complex: Characterization and induction of morphological abnormalities in pathogenic fungi

A cadmium complex of the general formula Cd(C₁₃H₉O₂NCl)₂(H₂O)₂ {C₁₃H₉O₂NCl = 2-(4-chlorophenylamino)benzoate} was synthesized and characterized regarding its CHN data, solution molar conductivity and spectroscopic (UV–Vis. and IR) properties. Cadmium sulfide nanoparticles (CdS NPs) were grown form the microcrystalline complex and thiourea via a hydrothermal route. The as-prepared NPs were assigned based on X-ray powder diffraction (PXRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM) and Brunauer – Emmett – Teller (BET) surface area measurements. The CdS absorption and emission spectra were also recorded that revealed an energy gap of 2.47 eV and large Stokes shift of 130 nm. For the as-prepared NPs, the measurements have also indicated a mesoporous structure and an average particle size of 20–28 nm associated with an average pore diameter of 11.21 nm. The as-synthesized CdS NPs acted as antifungal controlling agent against human and plant pathogenic fungi of serious environmental and health concerns. The NPs at concentration of 200 ppm inhibited several fungi with inhibition efficiency of 100% against Aspergillus ustus Au-28. The nanoparticles induced morphological abnormalities in fungal mycelia, conidia and vesicle. Additionally, they inhibited the conidia septum formation, accelerated the chlamydospores generation and enlarged the yeast cells.     

手性双官能硫族化合物催化烯烃的不对称亲电硫化反应

手性含硫化合物在药物化学和不对称合成领域中应用广泛,发展这类化合物的新合成方法是有机合成化学的重要任务.烯烃的不对称亲电硫化反应为手性含硫化合物的合成提供了一条方便的途径,通过这种方式不仅可以在烯烃母体分子上引入一个含硫基团,同时也能够引入另外一个重要的官能团.我们课题组设计、合成了一系列手性双官能硒醚/硫醚催化剂,并...     

Cu2ZnSnS4 类四元硫族半导体的理论研究——以二元、三元、四元半导体的演化为思路

在过去60多年中,人们对半导体的研究集中在一元、二元和三元半导体方面,最近,出于寻找新型廉价、环保、高效光伏转换材料的需要,Cu2ZnSnS4 类 I2-II-IV-VI4型四元硫族半导体吸引了人们越来越多的关注,它在光催化和热电等多方面的应用也不断被发掘. 然而,对于这类四元半导体的基本性质,如晶体结构和电子结构,人们知之甚少,很多研究还停留在经验阶段. 文章首先简要回顾了这类半导体的由来和在应用方面的最新进展,然后详细介绍了文章作者对这类四元半导体的第一性原理计算研究工作的进展,其中包括：系统研究了这类硫族半导体在从二元向三元再向四元的演化过程中晶体结构和电子能带结构变化的规律,总结了元素成分对其影响的一般趋势,并结合实验结果分析了这类四元半导体晶格结构表征和带隙测量中易于出现的混淆;文章作者还以Cu2ZnSnS4 为例,考察了这类四元化合物相对二元、三元化合物的相稳定性和本征缺陷性质. 文章介绍的研究结果将为一系列I2-II-IV-VI4型四元半导体的深入研究提供基础.     

Amorphous to crystalline phase transition in glassy Se65Te20Ag15 alloy

In the present work, the amorphous to crystalline phase transition of chalcogenide glass Se₆₅Te₂₀Ag₁₅ has been studied using differential scanning calorimetric (DSC) measurements. The heating rate dependence of crystallization peaks has been used for the determination of activation energies of glass transition (E _g) and crystallization (E _c). Different non-isothermal methods have been used for this purpose. Other useful kinetic parameters such as the order parameter (n), the numerical factor of crystallization mechanism (m) and the frequency factor (K _o) of the rate constant (K) have been also determined.     

Ga对新型远红外Te基硫系玻璃光学性能的影响

用传统熔融淬冷法制备了新型远红外Te基硫系玻璃(100-x)(GeTe₄)-xGa (x=0, 5, 10 mol%).利用差热分析(DTA)、可见/近红外吸收光谱、红外透射光谱等技术,在GeTe₄玻璃的基础上,通过引入较高配位金属Ga, 研究其对玻璃组成、结构和性能的影响,利用经典的Tauc方程计算了样品光学带隙允许的直接跃迁、允许的间接跃迁及Urbach能量.分析结果表明:在GeTe₄玻璃中引入 关键词： 光学材料 硫系玻璃 光学带隙 红外光谱     

中红外高保偏硫系玻璃双芯光子晶体光纤耦合特性研究

设计了一种中红外硫系玻璃双芯光子晶体光纤,利用多极法和模式耦合基本理论研究了这种光纤的耦合特性.数值模拟发现,空气孔间距Λ = 5.4 μm,空气孔半径为r = 1.35 μm,空气填充率d/Λ = 0.5的光纤,在归一化波长λ/Λ = 2.04 μm处双折射可以达到0.551×10^-2,在归一化波长λ/Λ = 0.93 μm处x偏振方向的耦合长度为145.32 μm,y偏振方向的耦合长 关键词： 双芯光子晶体光纤 硫系玻璃 双折射 耦合长度     

中红外色散平坦硫系光子晶体光纤设计及性能研究

本文以自制Ge20Sb15Se65硫系玻璃为基质材料,设计一种正八边形结构色散平坦型中红外硫系光子晶体光纤,并采用多极法对其中红外色散和传输特性进行数值研究.结果表明:控制该光纤占空比(d/Λ)在0.323—0.367之间,其色散及传输特性在3—5μm范围内可调.当孔间距Λ=3.4μm,孔直径d=1.1μm时,光纤在4.1—4.9μm波段的色散值在0.8—0.8 ps·nm 1·km 1波动,且具备单模低损耗传输(Loss0.049dB/m),小模场面积(Aeff8.46μm2)特性,适合于中红外非线性应用领域.     

Tm~(3+)掺杂Ge-Ga-S玻璃微球-石英光纤锥耦合系统的荧光回廊模特性

以熔融淬冷法自制了Tm~(3+)掺杂Ge-Ga-S硫系玻璃,并以此为基质材料,用漂浮粉料熔融法制备了直径分布为50—200μm的高品质因数(Q10~4)的有源硫系玻璃微球谐振腔.在显微镜下优选出一颗表面质量好、球形度较高、直径为72.84μm的微球,与氢氧焰扫描拉锥法制备的一根腰锥直径为1.93μm的石英光纤锥进行近场耦合.根据基质材料的吸收光谱特性,选用808 nm的半导体激光器作为抽运源.实验测得光纤锥倏逝波场激发出了掺Tm~(3+)硫系玻璃微球在1460 nm附近的荧光回廊模式,其典型共振峰间隔为4.39 nm.实验测得的荧光回廊模式与米氏散射理论计算结果符合度较高(最大误差仅为0.047%),验证了本文提出的掺Tm~(3+)硫系微球制备及耦合工艺的可行性.