Syntheses and crystal structures of copper mixed-ligand complexes of multidentate enaminones and acetate anions

Reactions of ferrocenoylacetone with 2-(aminomethyl)pyridine and N-(2-hydroxyethyl)-1,2-diaminoethane afford the multidentate enaminones HL¹ and H₃L², respectively. Reactions of copper acetate with the two enaminones generate the corresponding mixed-ligand complexes I and II, which are formulated as [CuL¹(OAc)] and [Cu(H₂L²)(OAc)], respectively. The structures of HL¹, I and II have been determined by single-crystal X-ray crystallography. In complex I, HL¹ acts as a monoanionic tridentate donor via the carbonyl oxygen, deprotonated enamine nitrogen and pyridyl nitrogen atoms, the acetate anion is monodentate and the coordination geometry of the central metal is square planar. In complex II, H₃L² is a monoanionic tetradentate ligand via the carbonyl oxygen, deprotonated enamine nitrogen, secondary amine nitrogen and hydroxy oxygen atoms, the acetate anion is monodentate and the coordination geometry of the central metal is a distorted trigonal bipyramid.     

Ge-Sb-Se硫系玻璃的折射率和热光系数

Ge-Sb-Se硫系玻璃被认为是极佳的红外传输材料和有潜力的非线性光学材料.在光学设计中,玻璃的线性折射率(n)及其热光系数(ζ)是关键技术参数.以预测和调控Ge-Sb-Se玻璃的n和ζ为目的,考察了玻璃的n,ζ,密度(d)和体积膨胀系数(β)与化学参数dSe和拓扑网络结构参数r的内在联系.研究发现,玻璃的n随d的增加而增大;ζ随β的增大而近似线性减小;β随dSe的减小或r的增大而减小;当Ge含量固定时, d随dSe的减小或r的增大而增大,当Sb含量固定时, d在dSe=0时具有最小值.基于实测d和n,拟合获得了Ge, Sb和Se元素在2—12μm波段的摩尔折射度(R_i),分别为R_(Ge)=10.16—10.50 cm~3/mol,RSb=16.71—17.08 cm~3/mol和RSe=11.15—11.21 cm~3/mol,根据d和R_i计算得到的n与实测值的偏差小于1%.基于实测ζ和β,拟合得到了Ge, Sb和Se元素在2—12μm波段的摩尔折射度温度系数(φ_i),分别为φ_(Ge)=21.1—22.6 ppm/K,φ_(Sb)=7.2—8.4 ppm/K和φ_(Se)=90.2—94.2 ppm/K,根据β和φ_i计算得到的ζ与实测值的偏差小于6 ppm/K.     

Why aggregated carbon nanotubes exhibit low quantum efficiency

Aggregation of carbon nanotubes reduces quantum efficiency and the phenomenon is found to be related to photocurrent leakage through oxygenated lattices acting as low barrier intertube channels. This outcome is supported by calculation and optical excitation experiments.     

Syntheses and crystal structures of two isomeric pyrazoles with ferrocenyl groups

Ferrocenoylacetone I reacts with terephthaloyl hydrazide in the presence of a catalytic amount of p-toluenesulfonic acid to afford complex 1 whereas acylation of 3(5)-ferrocenyl-5(3)-methylpyrazole II with terephthaloyl chloride leads to an isomer of complex 1, viz. complex 2. Two new complexes have been characterized by elemental analyses and IR,¹H NMR, UV spectra and structurally characterized by single-crystal X-ray crystallography. Complex 1 (C₃₆H₃₀Fe₂N₄O₂) crystallizes in the monoclinic space group P2₁/c, with lattice constants: a = 11.593(2) ?, b = 12.9962(17) ?, c = 10.0030(17) ?, β = 113.227(4)°, V = 1462.1(4) ?³, Z = 4, D _c = 1.505 g·cm⁻³, F(000) = 684, R ₁ = 0.0307, wR ₂ = 0.0739. Complex 2 (C₃₆H₃₀Fe₂N₄O₂) crystallizes in the monoclinic space group P2₁/n, with lattice constants: a = 12.2388(18) ?, b = 7.3200(15) ?, c = 17.288(4) ?, β = 90.89(3)°, V = 1466.9(5) ?³, Z = 2, D _c = 1.500 g·cm⁻³, F(000) = 684, R ₁ = 0.0410, wR ₂ = 0.1247. Supplementary material Full crystallographic data (CCDC No. 602174 for complex 1 and CCDC No. 602175 for complex 2) have been deposited at the Cambridge Crystallographic Database Centre and are available on request from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336-033; Email:deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).     

手性席夫碱及其金属配合物作为手性催化剂的某些应用

简要介绍和评述了近15年来手性Schiff碱及其金属配合物作为手性催化剂, 在不对称氢化、不对称氢转移、不对称氢硅化、不对称硅氰化和不对称氢氰化等反应中的应用研究进展.     

超级质子-质子对撞机中束流热屏的热-结构耦合模拟分析

束流热屏(beam screen)是新一代高能粒子对撞机中的重要部件,用于将束流在管道中运行时产生的热量转移到冷却系统中,同时通过束流热屏上的排气孔将残余气体输送至冷管壁上,维持良好的真空度.然而,在转移热负载的过程中,温度变化产生的形变会影响束流热屏的结构稳定性.如何在保证束流热屏良好传热性能的情况下,尽量减小形变是优化束流热屏结构设计的关键问题之一.本文采用ANSYS软件对束流热屏模型的传热性能和力学性能进行了模拟,并优化了束流热屏结构设计,增强其传热性能和结构稳定性.对于束流热屏外屏的内表面,采用减小铜涂层厚度的方式来降低运行过程中产生的洛伦兹力.相关理论模型计算结果表明:与厚度为100μm的铜涂层工况相比,当铜涂层的厚度在0到100μm之间变化时,厚度为75μm的铜涂层可以使束流热屏外屏的最大形变降低70.9%,同时使束流热屏的最高温度升高1.1%.对于束流热屏内屏,采用间隔布置支撑肋片的设计方案对束流热屏的结构进行加固处理,提高束流热屏整体的结构稳定性.计算结果表明:与未加支撑肋片的工况相比,当相邻两个支撑肋片之间的间隔为1个排气孔时,束流热屏内屏的最大形变可降低86.8%,同时使束流热屏的最高温度降低7.69%.研究成果为新一代高能粒子加速器真空系统中关键部件束流热屏的设计提供重要的理论参考.     

Determination of trans-fatty acids in food samples based on the precolumn fluorescence derivatization by high performance liquid chromatography

Trans-fatty acids are unsaturated fatty acids that are considered to have health risks. 1,3,5,7-Tetramethyl-8-butyrethylenediamine-difluoroboradiaza-s-indacene is a highly sensitive fluorescent labeling reagent for carboxylic acids developed by our lab. In this study, using this precolumn fluorescent derivatization reagent, a rapid and accurate high-performance liquid chromatography with fluorescence detection method was developed for the determination of two trans-fatty acids in food samples. Under the optimized derivative conditions, two trans-fatty acids were tagged with the fluorescent labeling reagent in the presence of 1-ethyl-3-(3-dimethyl-aminopropyl) carbodiimide at 25°C for 30 min. Then, the baseline separation of trans- and cis-fatty acids and their saturated fatty acid with similar structures was achieved with less interference using a reversed-phased C₁₈ column with isocratic elution in 14 min. With fluorescence detection at λ_ex/λ_em = 490 /510 nm, the linear range of the TFAs was 1.0-200 nM with low detection limits in the range of 0.1–0.2 nM (signal-to-noise ratio = 3). In addition, the proposed approach was successfully applied for the detection of trans-fatty acids in food samples, and the recoveries using this method ranged from 96.02 to 109.22% with low relative standard deviations of 1.2–4.3% (n = 6).     

Syntheses,crystal structures,and electrochemical studies of dinuclear coordination compounds with the Fe2(CO)6 core

Reaction of 2-C₅H₄ NCOSPh, generated from 2-C₅H₄NCO₂H and PhSH in the presence of DCC, with Fe₃(CO)₁₂ affords (μ-κ²C,N-2-C₅H₄N)(μ-PhS)Fe₂(CO)₆ (1) and (μ-PhS)₂Fe₂(CO)₆ (2). Reaction of (NC)₂C=C(SMe)₂, formed from NCCH₂CN, CS₂, and MeI in the presence of NaOH, with Fe₃(CO)₁₂ provides (μ-κ²C,S-(NC)₂C=CSMe)(μ-MeS)Fe₂(CO)₆ (3) and (μ-MeS)₂Fe₂(CO)₆ (4). All complexes have been fully characterized by EA, IR, ¹H NMR, and ¹³C NMR spectroscopy and structurally determined by X-ray crystallography. In 1 and 3, the group attached to the bridging S is at the equatorial position. In 2, two phenyl groups are at equatorial positions. Two isomers of 4, ae-4 and ee-4, can be separated by thin-layer chromatography. DFT calculations reveal that the Gibbs energy difference between ae-4 and ee-4 is ?2.17 kcal mol^?1 in THF and ?2.29 kcal mol^?1 in benzene, and the isomerization barrier between ae-4 and ee-4 is 14.92 kcal mol^?1 in THF and 16.84 kcal mol^?1 in benzene. All these results suggest that ae-4 is more stable than ee-4 in either THF or benzene, and the two isomers do not interconvert. Electrochemical studies of 1 and 3 demonstrate that using HOAc as a proton source 1 and 3 can catalyze H₂ production.     

Syntheses and Crystal Structures of Two Ferrocenyl Dicarboximides

Abstract  

Reactions of 1,1′-ferrocenedicarboxylic chloride with 2-aminopyrimidine and 2-aminopyrazine produce organometallic dicarboximides I and II, respectively. They crystallize in space groups F dd2 and P2₁/c, respectively. The molecules of I lying on twofold rotation axes are linked into a B-faced sheet by a C–H···O=C hydrogen bond [H····O = 2.46, C···O = 3.163(7) ? and C–H···O = 132°]. The sheets are linked into a layered structure by two types of weak C–H···O=C hydrogen bonds [H···O = 2.71, C···O = 3.340(8) ? and C–H···O = 126°; H···O = 2.69, C···O = 3.303(10) ? and C–H···O = 124°]. The molecules of II are linked into a centrosymmetric R ₂²(12) dimer by a C–H···O hydrogen bond [H···O = 2.40, C···O = 3.321(10) ? and C–H···O = 172°]. The dimers are further packed along the a axis by a C–H···O hydrogen bond [H···O = 2.69, C···O = 3.416(9) ? and C–H···O = 135°] to give an [100] double-chain. The double-chain is packed in the [010] direction by a C–H···O=C hydrogen bond [H···O = 2.69, C···O = 3.532(9) ? and C–H···O = 150°]. Further the intermolecular C–H···N hydrogen bond involving the cyclopentadienyl group as a hydrogen-bond donor and pyrazine N atom as an acceptor [H···O = 2.71, C···N = 3.536(10) ? and C–H···N = 148°] leads to a three-dimensional framework structure.