Synthesis of substituted indenyl lanthanide chloride and molecular structure of [(C5H9C9H6)(2)Yb(mu-Cl)(2)Li(Et2O)(2)]

Reaction of anhydrous ytterbium trichlorides with 2 equiv. of cyclopentylindenyl lithium in THF solution, followed by removal of the solvent MO. crystallization of the product from diethyl ether, affords a crystal complex of the composition (C5H9C9H6)(2)Yb(mu-Cl)(2)Li(Et2O)(2). Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenyl rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb, U and two chlorine atoms form a plane.

Synthesis and structure of iron complex with 1,2-dithiolate-1,2-dicarba-closo-dodecaborane [Li(THF)(4)][Fe(S2C2B10H10)(2)(THF)]

The crystal of complex [Li(THF)(4)][Fe(S2C2B10H10)(2)(THF)] 3 belongs to monoclinic, space group P2(1) with a = 11.964(2), b = 16.527(3), c = 12.554(3) Angstrom,beta = 108.70(3)degrees, V= 2351.3(8) Angstrom(3), Z = 2, M-r = 835.95, D-c = 1.181 g/cm(3), mu (MoKalpha) = 5.30 cm(-1), f(000) = '874, R = 0.0622 and Rw 0.1538 for 1641 observed reflections with I > 2sigma(I). The ionic complex,of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)(2)(THF)](-) and the tetrahedral cation of [Li(THF)(4)](+). The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.

Synthesis and crystal structure of cyclopentylindene rare earth complex (C5H9C9H6)(3)SMCl-Li+ (THF)(4)

Rare earth complex (C5H9C9H6)(3)SmCl-Li+ (THF)(4)( I ) was synthesized by reacting anhydrous SmCl3 with two equivalents of C5H9C9H6Li. From mix-solvent of THF and hexane, red color single crystals were obtained. The crystal belongs to a cubic system, space group P2(1)3 with unit cell parameters a= b=c= 1. 754 0(2) nm, alpha=beta=gamma=90degrees, V=5. 396 4(11) nm(3), Z = 4. The ten-coordinated samarium atom is bonded to three cyclopentylindenyl rings and a chlorine atom to form the anionic part of the title complex, ring centroids and the chlorine atom form a tortured tetrahedron around samarium. In the cationic part, lithium atom coordinates to four oxygen atoms of THF molecules to form a normal tetrahedron. The Sm-C(within the same ring) distance varies from 0. 268 to 0. 299 nm.

三(环戊基茚基)钐配合物(C_5H_9C_9H_6)_3SmCl~-Li~+(THF)_4的合成与晶体结构

稀土配合物能使极性和非极性单体聚合[1] .虽然目前已测定了几乎所有的三 (环戊二烯基 )稀土配合物及部分三 (取代环戊二烯基 )稀土配合物的晶体结构 ,但有关三 (茚基 )稀土配合物的报道较少 .第一个三 (茚基 )稀土配合物是无水三氯化稀土与 3倍物质的量的茚基钠 C9H7Na在四氢呋喃中反应而得 ,但未报道其晶体结构[2 ] .后来用同样的反应却分离出以氯为桥的二聚体离子对配合物[Na( THF) 6][Ln( η5- C9H7) 3μ( Cl) Ln( η5- C9H7) 3]( Ln=Nd,Sm) [3] .无水三氯化稀土与 Mg( C9H7) 2 或C9H7K等物质的量反应则生成非溶剂化的 ( C9H7) 3Sm[4 ] ,而与茚基钠和环辛四烯钾 ( C8H8K)以 1∶ 2∶ 1物质的量比反应时 ,则得到 ( C9H7) 3Ln( THF) ( Ln=Nd,Gd) [5] .Bottomley[6] 曾用 ( C9Me7) K(七甲基茚基钾 )与 L n Cl3(物质的量比 3∶ 1 )反应制备 ( C9Me7) 3Nd( THF) 5和 ( C9Me7) 3Er· ( THF) 3,但未报道晶...

Preparation, structure and luminescence of BaMAl10O17 : Eu2+ (M = Be, Mg, Ca, Zn, Cd, Mn, Co, Li) system

The BaMA(10)O(17) (M = Be, Mg, Ca, Zn, Cd, Mn, Co, Li) system has been synthesized by solid state method and characterized by XRD. The results show that when M is Mg, Zn, Mn, Co, Li, there exists the structure of beta-Al2O3 for BaMAl10O17 system, and when M indicates Cd, beta-Al2O3 structure is formed accompanying alpha-Al2O3 phase, and when M represents Be and Ca, beta-Al2O3 structure cannot be formed. This demonstrates that the condition forming beta-Al2O3 structure compounds for the system BaMAl10O17 is 0.05nm < R-M < 0.09nm (R-M represents the radius of M). The thought that if a M ion can form a stable spinel structure there exsits a corresponding magnetoplumbite and beta-alumina structure is proposed for BaMAl10O17 system according to the experimental results. When M is Li, Be, Zn, Eu2+ activator produces an emission of nearly 450 nm with half height width about 50 nm, when M is Mn, there are simultaneously the emissions of Eu2+ and Mn2+ and the excitation energy of Eu2+ can transfer to Mn2+ in the host, when M is Cd, Eu2+ displays a double-emission band, which can be explained by the Jahn-Teller's effect. It is possible for the system BaMAl10O17 with M being Li, Be, Zn to become blue-emitting component in three colour lamp through further study.

BaMAl_(10)O_(17)(M=Be,Mg,Ca,Zn,Cd,Mn,Co,Li)体系的合成、结构和Eu~(2+)在其中的发光

在BaMAl10O17 体系中 ,将M扩大到除镁以外的其它离子 ,研究和讨论了离子半径与基质结构的形成关系 ,提出能稳定(形成)尖晶石结构的M离子有相应的磁铅矿或β Al2O3 结构的化合物存在的思想 ,并研究了Eu2 +在体系中的发光性能。结果表明 ,M=Zn,Cd,Mn,Co,Li时可形成 β Al2O3 结构化合物 ,M=Ca,Be时不能形成这类结构 ,Ca形成多相共存 ,Be形成一未知相 ;Eu2 +在M=Li,Be,Zn体系中具有良好的发光性能 ,发射波长450nm ,半高宽在50nm附近 ,将是一类很有前途的新的蓝色发光材料 ,Eu2 +在M=Mn的体系中存在Eu2 +和Mn2 +的同时发射 ,在M=Cd体系中 ,Eu2 +产生一双重宽带发射。对实验结果进行了合理的解释

ABF_3:Eu,Gd(A:K,Li;B:Ba,Mg)中Gd~(3+)→Eu~(2+)的能量传递

通过高温固相反应法,在高纯N_2气氛中合成了BaLiF_3,KMgF_3中单掺和双掺Eu,Gd的ABF_3型复合氟化物。研究了各类掺杂体系的光谱特性,观察到了Gd~(3+)→Eu~(2+)的能量传递,分析了能量传递过程,探讨了能量传递机理,并讨论了Gd~(3+)和Eu~(2+)的取代格位。

Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF)(6)](2)[(Cp6Sm6Se13)-Sm-t] and [Li(LHF4](2)[Cp6Nd6Se13]

The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp ' Ln(THF)](2)(mu (2)-Cl)(2)(mu (3)-Cl)(3)Na(THF)}(n) [Cp ' = eta (5)-' BuC5H4; Ln = Nd (1a), Sm (1b), Gd (1c), Yb (1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl(3), with NaCp ' in THF solution. Complex 1b reacts with Na2Se5 to give hexanuclear samarium polyselenide complexes [Na(THF)(6)](2)[Cp-6' SM6(mu (6)-Se)(mu -Se-2)(6)] (2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF)(4)](2)[Cp6Nd6(mu (6)-Se)(mu -Se-2)(6)] (3) is synthesized by the reaction of [CpNdCl2. 2LiCl . 5THF] with Na2Se5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms. (C) 2001 Elsevier Science BN. All rights reserved.

Synthesis and structure of a novel mononuclear tungsten (VI) citrato complex, (NH4)(3)[Li(H2O)(3)WO3(C6H4O7)]

The first mononuclear tungsten-citrato complex, (NH4)(3)[Li(H2O)(3)WO3(C6H4O7)] (1) has been prepared by the reaction of ammonium tetrathio tungstate and lithium citrate in CH3OH - H2O solution at pH 8.2. There are two crystallographically independent anions in the asymmetric crystallographic unit. The crystal structure of the title compound (triclinic, space group P (1) over bar, a = 6.901(1), b = 15.136(3), c = 16.107(3) Angstrom, alpha = 75.85(3), beta = 89.89(3), gamma = 89.97(3), V = 1631.4(6) Angstrom (3), R = 0.068, R-w = 0.1674 for 3878 reflections with I > 2 sigma (1)), reveals that in the compound a tungsten atom is coordinated to a fully deprotonated citrate as a tridentate ligand and three terminal oxygen atoms to form a distorted coordination octahedron.

Synthesis and crystal structure of (1,3-(Bu2C5H3)-Bu-t)(2)Sm(mu-Cl)(2)Li(THF)(2)

Anhydrous SmCl3 reacts with two equal of Li(1-3-(Bu2C5H3)-Bu-t) to give a complex (1,3-(Bu2C5H3)-Bu-t)(2) Sm(mu -Cl)(2)Li(THF)(2) (C34H58Cl2LiO2Sm, M-r = 726.99), monoclinic, space group P2(1)/n, a = 10.615(2), b = 21.037(4), c = 17.166(3) Angstrom, beta = 93.60(3)degrees, V = 3825.7 (13) Angstrom (3), Z = 4, D-c = 1.262 Mg/m(3), mu = 1.699 mm(-1) and F(000) = 1508, final R = 0.0387 and wR = 0.0741 for 5320 observed[I greater than or equal to2 sigma (I)] reflections. The average Sm - C distance is 2.73 Angstrom. Sm - Cl1 and Sm - Cl2 distances are 2.719 (2) and 2. 697 (2) Angstrom, respectively. Two 1, 3-(Bu2C5H3)-Bu-t-ring centroids and two mu (2)-bridging chloride atoms around Sm atom form a distorted tetrahedron.

Analysis of structural relaxation in a Li(2)O2SiO(2) glass using rate heating approach

The structural relaxation process of an inorganic glass (Li(2)O2SiO(2)) at different cooling rates has been studied by differential scanning calorimetry. A four-parameter model-Tool-Narayanaswamy-Moynihan (TNM) model was applied to simulate the normalized specific heat curve measured. Four parameters, Delta h*/R, beta, In A, and x were obtained and compared with the values obtained from the isothermal approach. (C) 1999 Kluwer Academic Publishers.

Eu~(2+)激活的Li-β-Al_2O_3的组成、结构和发光

运用周期表对角线规则，获得了Eu2+激活的Li-β-Al2O3新的发光基质，研究了该基质的组成、结构、电荷补偿机制及Eu2+在体系中的发光性能结果表明：锂对BaMgAl10O17基质中镁的取代仍然保持β-Al2O3结构不变，Li-β-Al2O3基质中的电荷补偿主要是形成间隙Al3+或Li+离子机制，Eu2+激活的Li-β-Al2O3具有良好的发光性能，通过进一步研究有可能应用到三基色发光材料中去

A phenomenological study of the structural relaxation of an inorganic glass (Li(2)O2SiO(2))

The structural relaxation process of an inorganic glass (Li(2)O2SiO(2)) has been studied by differential scanning calorimetry. The sample is subjected to different thermal ageing histories with isothermal stages at an ageing temperature of T-g - 30 degrees C for different ageing times and at an ageing time of 16 h for different ageing temperatures. A four-parameter Tool-Narayanaswamy-Moynihan (TNM) model, is applied to simulate the normalized specific-heat curves measured. The ageing-temperature and ageing-time dependence of the structural relaxation parameters in the TNM model is obtained. (C) 1998 Elsevier Science S.A. All rights reserved.

The role of Li-O bonds in calculations of nonlinear optical coefficients of LiXO3-type complex crystals

The second-order nonlinear optical (NLO) tenser coefficients of LiXO3 (X = I; Nb or Ta) type complex crystals have been calculated using the chemical bond theory of complex crystals. Contributions of each type of bond to the total second-order NLO coefficient d(ij) and the linear susceptibility X are quantitatively determined. All tensor values thus calculated are in good agreement with experimental data. The Li-O bonds are found to be an important group in the contributions to the total NLO tenser coefficient, especially for those in LiNbO3 and LiTaO3. The importance of Li-O bonds depends on the environment of Li atom in these crystals.

Extraction and separation of heavy rare earth (III) with Extraction Resin containing di(2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272)

Extraction resins, of the type of;levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50 degrees C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm2O3 >99.97%, >80%, Er2O3 >99.9%, >94% and Yb2O3 >99.8%, >80% respectively, have been obtained from a feed having the composition Tm2O3 60%, Er2O3 10%, and Yb2O3 3%, the others 27%. The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.