(μ-FcC≡CH)Co2(CO)6簇合物羰基取代衍生物的合成和分子结构

The substituted reactions of (μ-FcC≡CH)Co₂(CO)₆ with PPh₃, AsPh₃ and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, ¹H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co₂(CO)_6-nL[n=1, L=PPh₃（2）, AsPh₃（3）; n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P2₁/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm³, Z=4, F(000)=1 480, D_c=1.515 g·cm^-3, μ=15.62 cm^-1; final R indices [I > 2σ(I)]: R₁=0.040 9, ωR₂=0.076 9; S=1.007, Δρ_max=463e·nm^-3, Δρ_min=-395 e·nm^-3. The cluster 3 crystallizes in monoclinic, space group P2₁/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm³, Z=4, F(000)=1 552, D_c=1.574 g·cm^-3, μ=24.87 cm^-1; final R indices[I> 2σ（I）]：R₁=0.0437, ωR₂=0.078 2; S=0.995, Δρ_max=530 e·nm^-3, Δρ_min=-444 e·nm^-3. CCDC: 221860, 2; 221863, 3.     

锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

DBBD及其Cu(I)配位聚合物[CuI(DBBD)2]n的合成

In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(I) coordination polymer [CuI(DBBD)₂]_n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P2₁, and a=0.881 30(19) nm, b=1.966 0(6) nm, c=1.478 1(4) nm, β=119.429(12)°, V=2.230 5(10) nm³, D_c=1.276 g·cm^-3. The crystal 2 belongs to orthogonal system with space group Fmm2, and a=2.044 41(17) nm, b=1.543 06(13) nm, c=1.652 45(13) nm, V=5.212 9(7) nm³, D_c=1.669 g·cm^-3, Z=8. CCDC: 292931, 1; 292934, 2.     

新型一维Cd(Ⅱ)配位聚合物的合成、晶体结构和光致发光性质

A new 1D chain coordination polymer [Cd(dpq)(ox)_0.5Cl]_n(1) (dpq=dipyrido[3,2-d:2′,3′-f]quinoxaline and ox=oxalate) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and single crystal X-ray diffraction analysis. Compound 1 (CdClC₁₅H₈N₄O₂): monoclinic, space group P2₁/c, a=0.854 04(5) nm, b=2.094 90(13) nm, c=0.839 22(5) nm, Z=4, V=1.438(15) nm³, M_r=424.11, D_c=1.959 g·cm^-3, F(000)=828.0, μ=1.719 mm^-1, S=1.028, the final R=0.025 8 and wR=0.057 5. The crystal structure analysis indicates that the cadmium ion is coordinated by two oxygen atoms from a oxalate, two chelating nitrogen atoms from a dpq molecule and two Cl^- anions. The adjacent Cd(Ⅱ) ions are linked by Cl^- anions and oxalate ligands in alternate sequence to form a 1D chain coordination polymer and the adjacent chains are further connected by π-π stacking interactions to form a 2D supramolecular network. Moreover, the title compound exhibits blue emission in the solid state at room temperature. CCDC: 680748.     

配合物[CdCl(HL)(dpp)(H2O)]n·nH2O的合成、晶体结构与荧光性能研究

Under hydrothermal condition, the reaction of 3-hydroxy-1-adamantaneacetic acid (H₂L) with CdCl₂ and 1,3-di-4-pyridylpropane (dpp) has afforded a new Cd(Ⅱ) compound, [CdCl(HL)(dpp)(H₂O)]_n·nH₂O(1), which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is triclinic, space group P1 with a=1.091 0(1) nm, b=1.131 8(1) nm, c=1.246 4(1) nm, α=88.52(1)°, β=71.34(1)°, γ=68.11(1)°, V=1.345 2(1) nm³, Z=2, M_r=591.40, F(000)=608, D_c=1.460 g·cm^-3, μ=0.947 mm^-1, the final R=0.040 1 and wR=0.104 0 for 4 950 observed reflections (I>2σ(I)). Complex 1 consists of one-dimensional chains deriving from CdCl(HL)(H₂O) units linked by dpp ligands, and lattice water molecules decorate between the chains. The O-H…O and O-H…Cl hydrogen bonds lead to the formation of a 2D layer structure. CCDC: 756099.     

鼓形有机锡氧簇合物[nBuSn(O)(NNA)]6的合成、晶体结构及生物活性

The title complex [ⁿBuSn(O)(NNA)]₆(1), was synthesized by the reaction of ⁿBuSn(O)OH with naphthalene acetic acid in 1∶1 molar radio, where HNNA=naphthalene acetic acid. The complex was characterized by IR, ¹H NMR spectra and elemental analysis. The crystal structure was determined by X-ray diffraction method. It crystallizes in monoclinic system with space group P2₁/n. The crystal data are: a=2.647 1(5) nm, b=1.412 9(3) nm, c=2.805 7(6) nm, β=116.185(3)°, Z=4, V=9.417(3) nm³, D_c=1.595 g·cm^-3, μ=1.632 mm^-1, F(000)=4 512, R₁=0.050 3, wR₂=0.131 2. The structure shows a distorted octahedral configuration with six-coordination for the central tin atom. The bioactivity test shows that the Sn(Ⅳ) complex has selective antibacterial property. CCDC: 752497.     

μ-氧-双{三[邻氯(氟)苄基]锡}的合成、结构和量子化学研究

The tri(o-chlorobenzyl)tin chloride as well as the tri(o-fluorobenzyl)tin was treated with aqueous solution of NaOH to formed the μ-oxygen-bis[tri(o-chlorobenzyl)tin] and μ-oxygen-bis[tri(o-fluorobenzyl)tin], respectively. The crystal and molecular structures of compound were determined by X-ray diffraction. The crystal(1) belongs to triclinic space group P1 with a=1.0195(5), b=1.0951(6), c=1.0986(6)nm, α=118.250(7), β=104.923(7), γ=99.534(8)°, V=0.9827(9)nm³,Z=1, D_x=1.701g·cm^-3, μ(MoKα)=17.12cm^-1, F(000)=498, R₁=0.0680, wR₂=0.13014. The crystal(2) are triclinic, space group P1 with a=0.9635(3), b=1.0797(4), c=1.0852(3)nm, α =105.807(5), β=90.551(6), γ=116.382(5)°, V=0.9619(6)nm³, Z=2, D_x=1.595g·cm^-3, μ(MoKα)=13.62cm^-1, F(000)=458, R₁=0.0268, wR₂=0.0674. The bond lengths of Sn-C is 0.2128(9)～2.162(12)nm and 0.2155(4)～0.2162(3)nm, and the Sn-O is 0.1901nm and 0.19166(6)nm, respectively. The bond angle Sn-O-Sn is 180.0(0)°. The tin atom has a distorted tetrahedral geometry. The composition characteristics of some frontier molecular orbitals have been investigated by means of G98W package and taking Lanl2dz basis set. (1) CCDC:184751,(2) CCDC:187572.     

Ag(Ⅰ)、Pd(Ⅱ)异核金属簇合物的制备和晶体结构研究

The complexes of [Ag₂Pd₂(μ-dppm)₂(μ-S₂CNC₄H₈)₂(μ₃-S₂CNC₄H₈)₂](SbF₆)₂·Et₂O (1) and [AgPd(S₂CN C₄H₈)(μ-dppm)₂](SbF₆)·H₂O (2)were synthesized and their single crystal structures were determined by X-ray diffraction. The complex 1 is monoclinic system, space group P2₁/c with a=1.14370(3)nm, b=1.39025(4)nm, c=2.93579(8)nm, β=95.173(1)°, V=4.6490(2)nm³, Z=4, D_c=1.716g·cm^-3, μ(Mo Kα)=1682cm^-1, F(000)=2384, M_r=2401.98, R=0.0662, wR=0.1302. The complex 2 is monoclinic system, space group Cc with a=2.74136(6)nm, b=1.04317(2)nm, c=2.523990(10)nm, β=95.173(1)°, V=4.6490(2)nm³, Z=4, D_c=1.716g·cm^-3, μ(Mo Kα)=1682cm^-1, F(000)=2384, M_r=2401.98, R=0.0662, wR=0.1302. CCDC: 1, 213613; 2, 213612.     

二(o-氟苄基)锡双(四氢吡咯二硫代氨基甲酸酯)和二(p-氯苄基)锡双(二甲基二硫代氨基甲酸酯)的合成、表征及晶体结构

Di(o-fluorbenzyl)tin bis(dithiotetrahydropyrrolcarbamate) (1) and di(p-chlorbenzyl)tin bis(dithiomethylcarbamate) (2) were synthesized. Their structure were characterized by elementary analysis, IR and ¹H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of complex 1 belongs to orthorhombic with space group Pccn, a=2.096 1(12) nm, b=1.018 5(6) nm, c=1.205 9(7) nm, Z=4, V=2.574(2) nm³, D_c=1.624 g·cm^-3, μ(MoKα)=1.348 mm^-1, F(000)=1 272，R₁=0.038 7, wR₂=0.088 5. The crystal of complex 2 belongs to monoclinic with space group C2/c, a=1.531 3(16), b=1.868 4(19), c=0.951 8(10) nm, β=112.602(14)°, Z=4, V=2.514(5) nm³, D_c=1.612 g·cm^-3, μ(MoKα)=1.572 mm^-1, R₁=0.025 4, wR₂=0.070 4. In the complexes 1 and 2, the structures consist of discrete molecules containing six-coordinate tin atom in a distorted octahedron configuration. In crystal of complex 1, molecules are packed in the unit cell in one-dimensional chain structure through a S…S interaction between adjacent molecule. CCDC: 225420, 1; 225421, 2.     

μ-氧-双[三(对氟苄基)锡]的合成、表征及晶体结构

The μ-oxygen-bis[tri(p-fluorobenzyl)tin] was synthesized. The structure were characterized by elementary analysis, IR and ¹H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of the title compound belongs to rhombohedral with space group R, a=1.346 4(4), b=1.346 4(4), c=1.772 9(7) nm, α=90°, β=90°, γ=120°, Z=3, V=2.783 2(15) nm³, D_c=1.625 g·cm^-3, μ(Mo Kα)=1.408 mm^-1, S=1.088, F(000)=1 350, R₁=0.027 5, wR₂=0.065 9. In compound, the tin atom has a distorted tetrahedral coordination configuration. CCDC: 257079.     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

含茂基苯并三氮唑基镧系有机配合物的合成及表征

三茂基镧系化合物和苯并三氮唑在四氢呋喃中反应,合成了7个未见文献报道的含茂基苯并三氮唑基镧系有机配合物,经元素分析、IR和MS测定,从有关数据推测了这类配合物的可能结构。     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。