12,52-二羟基-15,55-二甲基-14,16,34,36,54,56,74,76-八硝基-2,4,6,8-四氧桥连-1,3,5,7（1,3）-杯[4]芳烃的合成

以1,5-二氟-2,4-二硝基苯和3,4,5-三甲氧基甲苯为起始原料,经环化、甲基化、硝化和去甲基化反应，合成了一种新型杯芳烃衍生物，其结构经¹H NMR，¹³C NMR，¹⁵N NMR和元素分析表征。      

Radiometrische Titrationen mit [60Co(CN)6]3?-Ionen

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Ce3+掺杂La2O3的17O固体核磁共振研究

本文用水热共沉淀法制备Ce³⁺掺杂La₂O₃的前驱体,随后在H₂/N₂气氛下用高温煅烧法合成了不同Ce³⁺浓度的掺杂La₂O₃。由于Ce³⁺的掺杂,¹⁷O固体核磁共振谱图中在698、650和558处出现了新的共振峰;随着Ce³⁺掺杂浓度的增加,这些峰的强度也随之增强。根据谱峰位置和强度,对谱图进行了归属:698、650处的共振峰应源自与Ce³⁺相连的四配位O(OCeLa₃),558处的信号则来自于与Ce³⁺相连的六配位O(OCeLa₅)。通过¹⁷O固体核磁共振能够直接观测与Ce³⁺直接相连的O显示该方法将可能用于研究稀土掺杂氧化物功能材料。     

Pr?zisions-Isotopenmessungen von 7Li/6Li

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Ein Gasz?hlrohr zur Messung von 14C- und 3H-Aktiyit?ten

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Unusual ion UO4? formed upon collision induced dissociation of [UO2(NO3)3]?, [UO2(ClO4)3]?, [UO2(CH3COO)3]? ions

The following ions [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ were generated from respective salts (UO₂(NO₃)₂, UO₂(ClO₄)₃, UO₂(CH3COO)2) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO₄ ⁻ ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U^VI compound, in which oxygen atoms bear unpaired electron and negative charge.     

F2 Σ+ -X 2Σ +Band System of Cobalt Carbide

The laser-induced fluorescence excitation spectrum of CoC was recorded in the spectral region from 13500 cm-1 to 22000 cm-1, in which the CoC molecules were produced by the reaction of sputtered cobalt atoms with methanol under supersonic jet cooled conditions. Much of the visible spectrum was assigned to transitions between the X2∑+ ground state and F2∑+ state. The 11 bands assigned as (v’=3-13, 0) transitions of the F2∑+- X2∑+ band system were observed and rotationally analyzed. Equilibrium constants for the F2∑+ state were Te=1362 cm-1, ωe=669 cm-1 ,ωe?e=4.3 cm-1, Be=0.546 cm-1, and Re=1.758A. Some new bands were observed.     

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

Ce3+掺杂La2O3的17O固体核磁共振研究

本文用水热共沉淀法制备Ce³⁺掺杂La₂O₃的前驱体,随后在H₂/N₂气氛下用高温煅烧法合成了不同Ce³⁺浓度的掺杂La₂O₃。由于Ce³⁺的掺杂,¹⁷O固体核磁共振谱图中在698、650和558处出现了新的共振峰;随着Ce³⁺掺杂浓度的增加,这些峰的强度也随之增强。根据谱峰位置和强度,对谱图进行了归属：698、650处的共振峰应源自与Ce³⁺相连的四配位O(OCeLa₃),558处的信号则来自于与Ce³⁺相连的六配位O(OCeLa₅)。通过¹⁷O固体核磁共振能够直接观测与Ce³⁺直接相连的O显示该方法将可能用于研究稀土掺杂氧化物功能材料。     

Synthesis and structure of gold and copper complexes: [Ph3PhCH2P]+[AuCl4]?, [NH(C2H4OH)3]+[AuCl4]? · H2O, and [Ph3EtP] 2+ [Cu2Cl6]2?

Triphenylbenzylphosphonium tetrachloroaurate (I) and triethanolammonium tetrachloroaurate hydrate (II) were prepared by reacting tetrachloroauric acid in acetone with triphenylbenzylphosphonium and triethanolammonium, respectively. Triphenylethylphosphonium hexachlorodicuprate (III) was synthesized from triphenylethylphosphonium chloride and copper chloride in acetone. The crystal structures of complexes I to III were determined by single-crystal X-ray diffraction. The phosphorus atoms in complex I have a nearly undistorted tetrahedral coordination (CPC, 108.3°–110.6°; P-C, 1.788–1.793 ?). The coordination of nitrogen atoms in the cations of complex II is a distorted tetrahedron (CNC, 111.7°–112.4°). The square coordination of aurum in I and II is only slightly distorted: the ClAuCl angles are 89.6°–90.3° (I) and 89.5°–90.6° (II) and the Au-Cl distances are 2.256–2.278 ? I) and 2.280–2.285 ? (II). The phosphorus atoms in complex III are tetracoordinated (CPC, 106.34°–111.73°; P-C, 1.790–1.795 ?). The copper atoms in III have a distorted tetrahedral coordination (ClCuCl, 98.48°–144.85°; Cu-Cl, 2.1999–2.3263 ?). The central fragment Cu₂Cl₂ in the anion of complex III is bent relative to the Cu₂ axis (the chlorine atom deviates from the Cu₂Cl plane by 0.27 ?).     

Synthesis and structure of the platinum complexes [Bu4N]+[PtBr5(DMSO)]?, [Ph4P]+[PtBr5(DMSO)]?, and [Ph3(n-Am)P]+[PtBr5(DMSO)]?

The complexes [Bu₄N]₂⁺[PtBr₆]²⁻ (I), [Ph₄P]₂⁺[PtBr₆]²⁻ (II), and [Ph₃(n-Am)P]₂⁺ (III) are synthesized by the reactions of tetrabutylammonium bromide, tetraphenylphosphonium bromide, and triphenyl(n-amyl)-tetraphenylphosphonium bromide, respectively, with potassium hexabromoplatinate (mole ratio 2: 1). After recrystallization from dimethyl sulfoxide, complexes I, II, and III transform into [Bu₄N]⁺[PtBr₅(DMSO)]⁻ (IV), [Ph₄P]⁺[PtBr₅(DMSO)]⁻ (V), and [Ph₃(n-Am)P]⁺[PtBr₅(DMSO)]⁻ (VI). According to the X-ray diffraction data, the cations of complexes IV–VI have a slightly distorted tetrahedral structure. The N-C and P-C bond lengths are 1.492(7)–1.533(6) and 1.782(10)–1.805(10) ?, respectively. The platinum atoms in the mononuclear anions are hexacoordinated. The dimethyl sulfoxide ligands are coordinated with the Pt atom through the sulfur atom (Pt-S 2.3280(18)–2.3389(11) ?). The Pt-Br bond lengths are 2.4330(6)–2.4724(6) ?.     

Separation of Yb as YbSO4 from the 176Yb target for production of 177Lu via the 176Yb(n, γ)177Yb→177Lu process

An effective and simple process for the separation of ¹⁷⁷Lu from neutron-irradiated Yb targets was developed. Irradiated Yb target was dissolved in H₂SO₄ solution and after reduction with sodium amalgam Yb was precipitated in the form of YbSO₄. From 50 mg of Yb irradiated target only 1 mg Yb remains in solution after precipitation and separation of YbSO₄. The overall recovery of ¹⁷⁷Lu is estimated at 73%. Further efficient chromatographic separation of carrier-free ¹⁷⁷Lu from 1 mg of Yb is relatively easy and is described in several papers.     

X-ray and conformation analysis of the new trinuclear cluster of osmium Os3(μ,η2-OCC6H5)(η3-C3H5)(CO)9

The crystal structure of the Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ cluster synthesized by the reaction of the (μ-H)Os₃(μ-O=CC₆H₅)(CO)₁₀ complex with allylamine in chloroform was determined by X-ray analysis. Prolonged storage of the reaction mixture led to N-C bond cleavage in allylamine and η³-addition of the allyl fragment at one of the Os atoms (Os-C 2.246 ?, 2.248 ?, and 2.273 ?). The unit cell parameters of the complex are a = 9.494(1) ?, b = 10.479(1) ?, c = 12.474(2) ?, α = 84.55(1)°, β = 70.08(1)°, γ = 70.72(1)°, V = 1255.8(4), ?³, space group P , Z = 2; C₁₉H₁₀O₁₀Os₃; d _calc = 2.922 g/cm³, 3085 I _hkl > 2σ _I of 3611 collected reflections; R = 0.0252. The structure of Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ is molecular. The plane of the Os₃ triangle and the OsCOOs plane are connected according to the “butterfly” principle with an angle of 103.4° between them. The Os-Os distances in the cluster core vary from 2.836(1) ? to 2.844(1) ?; the Os-C_carb distances are 1.88(1)–1.97(1) ?; the distances to the atoms of the bridging ligands are Os-C 2.11(1) ?, Os-O 2.14(1) ?; the O-C bridging bond is 1.24(1) ?. of the Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ triosmium cluster were studied theoretically. The potential curve of the internal rotation of the allyl ligand relative to the Os(1)-C(9) bond was determined. The rotation barrier of the allyl ligand in crystal relative to the Os(1)-C(9) bond is 8.38 kJ/mol, and the rotation of the ligand is not hindered. The effects of the intra-and intermolecular interactions on the conformation state of the cluster complex are considered. Original Russian Text Copyright ? 2008 by V. A. Maksakov, N. V. Pervukhina, N. V. Podberezskaya, M. Yu. Afonin, V. A. Potemkin, and V. P. Kirin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 5, pp. 926–932, September–October, 2008.     

Eu0.5RE0.5Fe0.5Mn0.5O3的57Fe Msosbauer谱研究

利用固相反应合成了Eu0.5RE0.5Fe0.5Mn0.5O3(RE=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Y)等化合物。测量了其XRD谱及57FeMssbauer谱。实验发现,随着RE原子序数的增加,样品的晶胞体积减小,Fe在化合物中处于Fe3+的高自旋状态,57Fe的四极裂矩与样品的畸变参数D成线性关系。     

13C NMR spectra of coordinated propargyl cations [Cp2Mo2(CO)4(μ-η2,η3-(HC≡CCR1R2)]+ BF4/?

A strong deshielding effect is observed for the carbon signal of carbocation center (C⁺) in the ¹³C NMR spectra of coordinated propargyl cations [Cp₂Mo₂(CO)₄(μ-η²,η³-(HC≡CCR¹R²)]⁺ BF₄⁻ (R¹ = R² = H) 1, (R¹ = Me, R² = H) 2, and (R¹ = R² = Me) 3 when hydrogen is replaced by methyl; the effect increases with the Mo-C⁺ distance (75.37, 98.3, and 148.68 ppm for compounds 1, 2, and 3, respectively). This indicates that the back-donation of electron density from the metal onto the ligand makes a substantial contribution to the stabilization of these cations. Original Russian Text ? I.V. Barinov, V.A. Chertkov, 2009, published in Vestnik Moskovskogo Universiteta. Khimiya, 2009, No. 1, pp. 29–34.     

BaLiF3:Ce 3+纳米粒子的制备及其光谱特性

BaLiF3属立方钙钛矿型复合氟化物, 作为高效闪烁晶体可用于热中子检测［1］. 由于其能带隙宽, 易于实现各种不同价态稀土离子掺杂, 可以获得许多可调谐性质, 因此它也是比较理想的光学功能材料的基质［2］. Ce3+激活的BaLiF3晶体作为紫外发射的短波固体激光材料和光放大材料的研究多有报道［3~5］     

O(1D)与CF3Br的反应研究

研究了CF     

新型微孔磷酸铝[C4N2H14]2+[H2Al3P3O14]2-的合成、结构及相转变

以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃.     

Zur Darstellung von 109Pd, 72Ga und 51Cr hoher spezifischer Aktivit?t zieht

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