Syntheses of (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, Er, Yb) and crystal structure of [(C_5H_9C_5H_4)_2-LnCl(THF)_n]_2(Ln=Sm, n=1; Ln=Er, n=0)

Reactions of lanthanoid trichlorides with sodium cyclopentylcyclopentadienyl in THFafford bis(cyclopentylcyclopentadienyl) lanthanoid chloride complexes (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, n=1; Ln= Er, Yb, n= 0). The compound [CP'_2SmCl(THF)]_2 (2) (Cp' =cyclopentylcy-clopentadienyl) crystallizes from mixed solvent of hexane and THF in monoclinic space group P_2_1/cwith a = 11.583 (3), b = 23.019(6), c = 8.227 (2), β= 90.26 (2)°, V= 2194 (1)~3, D_c= 1.59 g/cm~3.μ= 28.6 cm~(-1), F(000) = 1060, Z= 2 (dimers). Its crystal molecule is a dimer with a crystallographicsymmetry center. The central metal atom Sm is coordinated to two Cp' rings, two bridging chlorineatoms and one THF forming a distorted trigonal bipyramid. The crystal of [Cp'_2ErCl]_2 (3) belongs tothe triclinic space group P with a = 11.264 (2), b= 13.296(5), c = 14.296(6), a = 96.99 (3), β=112.47(2), γ= 102.78(2)°, V= 1865(1)~3, D_c= 1.67 g /cm~3, μ= 48.0 cm~(-1), F(000) = 924, Z = 2 (dimers).The molecule is a dimer consisting of two Cp'_2 ErCl species bridged by two Cl atoms. The centralmetal atom Er is coordinated to two Cp' rings and two bridging chlorine atoms forming a pseudo-tetrahedron. All these complexes are soluble in THF, DME, Et_2O, toluene and hexane.     

Synthesis, structures, and photoluminescence of heteroligand complexes Ln(L)(iso-Bu2PS2)2(NO3) (Ln = Sm, Tb, Dy; L = Phen, 2,2′-Bipy)

Heteroligand complexes Ln(L)(iso-Bu₂PS₂)₂(NO₃) (Ln = Sm, Tb, Dy; L = Phen, 2,2??-Bipy) (I?CVI) are synthesized. The structure of Dy(Phen)(iso-Bu₂PS₂)₂(NO₃) (III) is determined from the data of X-ray structure analysis. The crystal structure of complex III is based on discrete mononuclear molecules in which the Dy atom has distorted dodecahedral coordination (polyhedron N₂O₂S₄). The ligands Phen, iso-Bu₂PS ₂ ^? and NO ₃ ^? are bidentate-cyclic. According to the X-ray diffraction analysis data, complexes I and II are isostructural to compound III. Complexes I?CVI have photoluminescence in the visible spectral range. The photoluminescence spectra of solid samples of compounds I?CVI exhibit bands corresponding to the radiative electron transitions of the Sm³⁺, Tb³⁺, and Dy³⁺ ions. Among the studied compounds I?CVI, the Tb(III) complexes are characterized by the most intense photoluminescence.     

Hydrothermal Synthesis,Crystal Structures,and Fluorescence Properties of Ni(II)–Ln(III) Complexes (Ln = Sm,Pr, Eu)

Three novel 3d–4f heterometal complexes [Ln(NiL)₃(Btca)(NO₃)] · xH₂O (Ln = Sm(III) (I), Pr(III) (II), Eu(III) (III) (H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H₂Btca = benzotriazole-5-carboxylic acid) were solvothermally synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1555557 (I), 1555555 (II), 1555556 (III)). They crystallized in the monoclinic space group P2₁/n for I (x = 1.5) and C2/c for (II) and (III) (x = 1), respectively. In these complexes, the central Ln(III) and external nickel ions are bridged by macrocyclic oxamide groups. The metal center of Ln(III) resides in a distorted bicapped square antiprism surrounding with six oxygen atoms of three oxamide groups, two oxygen atoms of Btca^2– ion and two oxygen atoms of NO₃^-. Furthermore, there are C–H···O and/or C–H···N hydrogen bond interactions among nitrate, benzotriazole-5-carboxylate, macrocyclic oxamide and water to form three-dimensional superamolecular architecture. The fluorescence properties of the compounds I and II are also discussed.     

三元体系Ln(ClO~4)~3-ACAP-H~2O(Ln=La,Sm,Yb)的相平衡研究(30℃)

测定了三元体系Ln(ClO~4)~3-ACAP-H~2O(Ln=La,Sm,Yb, ACAP=4-乙酰安替比林)在30℃时的溶解度及饱和溶液的折光率,绘制了相应的溶度图和饱和溶液的折光率-组成图.体系的溶度曲线和折光率曲线均由三支组成,分别与ACAP,Ln(ACAP)~3(ClO~4)~3·nH~2O(Ln=La,n=4,Sm,2,Yb,2)和Ln(ClO~4)~3·nH~2O(Ln=La,n=8,Sm,9,Yb,8)相对应.从溶度图上发现了三个未见文献报道的三元化合物, 它们均为固液异组成溶解的化合物.通过化学分析,元素分析,TG-DTG,IR,UV和X射线粉末衍射进行了表征.初步探讨了影响安替比林4位酰代衍生物β-二酮配体配位能力的因素     

Reduction of LnIII to LnII in reactions of LnCl3·6H2O (Ln = Eu,Yb, and Sm) with Bui 2AlH in THF. The formation of soluble luminescent complexes LnCl2·xTHF

Soluble luminescent complexes of divalent lanthanides, LnCl₂·xTHF (Ln = Eu, Yb, and Sm), were obtained for the first time by reduction of Ln^III to Ln^II in reactions of the lanthanide trichloride hexahydrates LnCl₃·6H₂O with Buⁱ ₂AlH in THF. The photoluminescence spectra and other spectral characteristics of LnCl₂·xTHF were examined.     

(η~5-C_5H_5)Ln(η~8-C_8H_8)(THF)_n(Ln=Pr,Nd,Gd)的合成及(η~5-C_5H_5)Pr(η~8-C_8H_8)(THF)_2的晶体结构

自1969年首次报道稀土环辛四烯基化合物Eu(C_8H_8)和Yb(C_8H_8)的合成以来,相继合成K[Ln(C_8H_8)_2],[Ln(C_8H_8)Cl·2THF]_2和[Ln(C_8H_8)·2THF]等,还报     

(CH_3C_5H_4)_3Ln·THF(Ln=Sm,Ho,Tb,Yb)与环戊二烯生成(C_5H_5)_3Ln·THF的新反应

研究了(CH_3C_5H_4)_3Ln·THF (Ln = Sm,Ho,Tb,Yb)与环戊二烯高产率生成 (C_5H_5)_3Ln·THF的新反应。反应产物经过了元素分析、质谱和X射线的表征。产 物(C_5H_5)_3Ln·THF的特征结构参数,如五元碳环的碳原子与中心金属的平均距 离,五元碳环质心与中心金属距离,配位的四氢呋喃氧原子与中心金属距离,由于 “镧系收缩现象”,随着中心原子序数的增加而减小。     

甲基环戊二烯基希土二氯化物Cp′LnCl2·3THF(Ln=Sm-Er,Y)的合成和表征

本文通过无水三氯化希土与等摩尔的甲基环戊二烯基钠（Ｃｐ′Ｎａ）在四氢呋喃（ＴＨＦ）中反应，合成了八个新的中性甲基环戊二烯基希土二氯化合物Ｃｐ′ＬｎＣｌ２·３ＴＨＦ［Ｌｎ＝Ｓｍ（１），Ｅｕ（２），Ｇｄ（３），Ｔｂ（４），Ｄｙ（５），Ｈｏ（６），Ｅｒ（７），Ｙ（８）］，并研究了茂环上甲基取代基对一茂二氯希土配合物分子结构及稳定性的影响。元素分析、红外光谱和质谱鉴定结果表明这八个化合物都是溶剂化的单体结构，其中配合物７的结构还用单晶Ｘ射线分析确证。     

Syntheses, structure, and luminescent properties of novel hydrated rare earth borates Ln2B6O10OH4•H2O (Ln = Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Y)

Ln(2)B(6)O(10)(OH)(4)?H(2)O (Ln = Pr, Nd, Sm-Gd, Dy, Ho, and Y), a new series of hydrated rare earth borates, have been synthesized under hydrothermal conditions. A single crystal of Nd analogue was used for the structure determination by X-ray diffraction. It crystallizes in the monoclinic space group C2/c with lattice constants a = 21.756(4), b = 4.3671(9), c = 12.192(2) ?, and β = 108.29(3)°. The other compounds are isostructural to Nd(2)B(6)O(10)(OH)(4)?H(2)O. The fundamental building block (FBB) of the polyborate anion in this structure is a three-membered ring [B(3)O(6)(OH)(2)](5-). The FBBs are connected by sharing oxygen atoms forming an infinite [B(3)O(5)(OH)(2)](3-) chain, and the chains are linked by hydrogen bonds, establishing a two-dimensional (2-D) [B(6)O(10)(OH)(4)?H(2)O](6-) layer. The 2-D borate layers are thus interconnected by Ln(3+) ions to form the complex three-dimensional structure. Ln(2)B(6)O(10)(OH)(4)?H(2)O dehydrates stepwise, giving rise to two new intermediate compounds Ln(2)B(6)O(10)(OH)(4) and Ln(2)B(6)O(11)(OH)(2). The investigation on the luminescent properties of Gd(2-2x)Eu(2x)B(6)O(10)(OH)(4)?H(2)O (x = 0.01-1.00) shows a high efficiency of Eu(3+) f-f transitions and the existence of the energy transfer process from Gd(3+) to Eu(3+). Eu(2)B(6)O(10)(OH)(4)?H(2)O and its two dehydrated products, Eu(2)B(6)O(10)(OH)(4) and Eu(2)B(6)O(11)(OH)(2), present the strongest emission peak at 620 nm ((5)D(0) → (7)F(2) transition), which may be potential red phosphors.     

Synthesis, Characterization and Antimicrobial Activity of Potassium Hydro(benzoyl)(phthalyl)borate and Its Cobalt(II), Nickel(II), and Copper(II) Complexes

A new organoborate ligand, hydro(benzoyl)(phthalyl)borate has been synthesized as its potassium salt (KL) and treatment of KL with one equivalent of MCl2•6H2O gave complexes ML(H2O)x•Cl [x＝2, M＝Co(II), Ni(II); x＝1, M＝Cu(II)]. All compounds were characterized by elemental analysis, FTIR, 1H NMR, ESI MS, UV-Vis techniques, conductivity and magnetic data measurements. Spectroscopic results suggest a square planar geometry in the Cu(II) complex, while the Co(II) and Ni(II) complexes possess an octahedral geometry. Antibacterial activities (in vitro) of the ligand and its metal complexes were studied against two Gram positive (B. subtillis and B. magterium) and two Gram negative bacteria (E. Coli and S. boydi) at a single concentration (75 μg/mL) by using the Disc diffusion method. Antifungal activities (in vitro) were also checked for the compounds by using the same method against Candida albicans 10261, Penicillium sp. and Asperjillius niger., at a single concentration (50 μg/mL). The results showed that all the metal complexes, specially the nickel(II) complex, have higher antibacterial and antifungal activities than the corresponding potassium salt.     

Synthesis and structural characterization of lanthanide oxalate–oxydiacetate mixed-ligand coordination polymers {[Ln(oda)(H2O) x ]2(ox)} n ( x = 3 for Ln = La,Ce, Pr,Gd, Tb and x = 2 for Ln = Er)

Reactions of oxydiacetic acid (H₂oda) with lanthanide oxide, nitrate, chloride, and carbonate gave six lanthanide oxalate–oxydiacetate mixed-ligand coordination polymers {[Ln(oda)(H₂O) _x ]₂(ox)} _n [x = 3 for Ln = La, Ce, Pr, Gd, Tb, (1–5), and x = 2 for Ln = Er (6)]. Oxydiacetic acid is decomposed into oxalic acid in this reaction. In the crystal structures of 1–6, oxydiacetate and the lanthanides build a chain, and the oxalate groups bridge two chains to form 1-D double-chain ladder-shaped structures, connected by intermolecular hydrogen bonds to form a 2-D network structure. These compounds contain approximately 3.0 × 6.4 Ų channels along the c-axis. The infrared spectra and thermal behaviors of 1–6 are also investigated.     

Oxidation resistance of LnSiON powders (Ln=Y,Gd and La)

For application of LnSiON (Ln=Y, Gd and La) oxynitride materials, e.g. as host-lattices for lamp phosphors, oxidation resistance up to about 600 °C in air is a prerequisite. In this study we prepared LnSiON (Ln=Y, Gd and La) powders by solid state reaction and observed via TGA/DTA-experiments that most compounds are oxidation resistant up to 600 °C in air. The stability in air at high temperatures increases going from Ln₅(SiO₄)₃N, Ln₄Si₂O₇N₂, LnSiO₂N, Ln₂Si₃O₃N₄ to Ln₃Si₈O₄N₁₁. This is explained by an increasing cross-linking between the siliconoxygennitrogen tetrahedra in this sequence. For the lattices with less cross-linking between the siliconoxygennitrogen tetrahedra we observed that the oxidation resistance decreases slightly going from Y and Gd to La. For these lattices, also, an additional weight gain was observed during the oxidation reaction, which was higher than expected for complete oxidation. The additional weight gain was ascribed to an intermediate phase in which nitrogen retention takes place.     

Synthesis,crystal structure of Gd(H2O)(C2O4)2 · NH4 and of La(C2O4)2 · NH4. Characterization of the Ln(H2O)(C2O4)2 · NH4 with Ln=Eu…Yb

Single crystals of two lanthanide complexes, presenting similar formula Ln(H₂O)_x(C₂O₄)₂ · NH₄ with Ln=La, x=0 and Ln=Gd, x=1, have been prepared, in closed system at 200 °C. The gadolinium complex is bi-dimensional. A layer is built by the packing of the basic unit, [Gd(C₂O₄)]₄. The gadolinium atoms are related only by bischelating oxalate ligands, the ammonium ion and the water molecule (bound to the gadolinium atom) are localized into the interlayer space. The lanthanum complex is tri-dimensional. The basic building unit remains approximately the same and the packing of these units form a layer. However, within these units, the lanthanum atoms are related by either an oxalate ligand or an edge. Moreover, an oxalate ligand assumes the connection between the layers. The ammonium ion is localized into two sets of intersecting channels. Pure phase of the gadolinium complex has been prepared at 100 °C and extended to some lanthanide elements, Eu…Yb. As the size of the lanthanide ionic radius is decreasing, it is noticeable that the a unit–cell constant follows an expansion pattern while the others two follow an usual contraction one. The thermal behavior of this family shows that the anhydrous compounds are obtained and that some water molecule is sorbed during the cooling. Thus, the anhydrous compounds present a relatively open-framework with some small micropores.     

Synthesis and Characterization of 2-Decyl-DTPA and Its Gd(Ⅲ) Chelate

IntroductionGadoliniumchelatesareveryimportantbecauseoftheirpotentialbiologicalapplicationsintheareaofmagneticresonanceimaging(MRI) .Thegadoliniumchelateofdiethylenetriaminepentaaceticacid(DTPA )wasthefirstMRIcontrastagentinclinicaluse .How ever,Gd DTPA ,asanextracellularcontrastagent,hasnoliver specificity .Theintroductionofanaddi tionallipophilicsubstitutenttoanyoneofthefivemethylenesoftheaceticacidresiduesortoanyoneofthefourcarbonatomsofthebackboneinDTPAmaychangethetissuespecificity…     

Synthesis and Characterization of 2-Decyl-DTPA and Its Gd(Ⅲ) Chelate

The present paper covers the synthesis and the characterization of ligand 2-decyl-3, 6, 9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid, H5L, and its Gd(Ⅲ) chelate. The protonation constants for H5L(lgKHi=10.90, 8.50, 4.55, 2.92, 2.20) and the stability constant for GdL2- (lgKGdL2-=22.80) were determined by means of potentiometric titration. They are similar to the corresponding values of DTPA and Gd-DTPA, respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after the introduction of a linear chain decyl group into the terminal acetic acid residue of DTPA. The Gd(Ⅲ) chelate may be a potential contrast agent with liver-specificity for magnetic resonance imaging(MRI).     

Synthesis and Crystal Structure of [(ArO)2(THF)Sm(μ-OH)]2·2THF (Ar = C6H2-tBu3-2,4,6)

The title complex [(ArO)2(THF)Sm(μ-OH)]2·2THF (Ar = C6H2-tBu3-2,4,6) was obtained by the hydrolysis of divalent (ArO)2Sm(THF)3·THF in toluene. It crystallizes in monoclinic, space group P21/c with a = 14.7968(14), b = 18.6981(15), c = 16.8264(17) (A), β = 109.366(2)°, V = 4392.0(7) (A)3, Z = 2, C88H150O10Sm2, Mr = 1668.78, Dc = 1.262 g/cm3, F(000) = 1764 and μ(MoKα) = 1.377 mm-1. The final R and wR are 0.0318 and 0.0749, respectively for 9038 observed reflections with I > 2(σI). The complex possesses a dimeric structure with two centrosymmetric hydroxyl bridges. The samarium atom is coordinated by five oxygen atoms to form a distorted square pyramidal geometry with the average Sm-O(Ar) distance of 2.1757(19) (A). There are H-bond interactions be- tween the molecules.     

Synthesis, Spectroscopic, Thermal, and Structural Characterization of Complex Ferrocyanides KLnFe(II)(CN)6 ⋅ 3.5H2O (Ln = Gd-Ho)

Four new mixed metal cyanides of lanthanides (Ln = Gd-Ho) and iron with the general formula KLnFe(CN)₆ 3.5H₂O have been synthesized and characterized by chemical, infrared and thermal techniques. X-ray diffraction (XRD) analysis have shown that all the complexes have orthorhombic unit cells with space group Cmcm. Cyanide bridges link to nine coordinated LnN₆(H₂O)₃ groups to the octahedral FeC₆ groups. Cavities within the structure are occupied by uncoordinated zeolitic water molecules and potassium ions. The potassium cations form a pseudo-hexagonal 2D sublattice. Thermal decomposition involves two consecutive steps: dehydration and inorganic residue evolution to ternary oxides.     

Syntheses,structures, magnetic properties,and photoluminescence of compounds Ln(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (Ln = Sm,Eu, Tb,Dy, and Tm)

Five compounds of the composition Ln(2,2′-Bipy)(C₄H₈NCS₂)₃ · 0.5CH₂Cl₂ (Ln = Sm (I), Eu (II), Tb (III), Dy (IV), and Tm (V); 2,2′-Bipy = 2,2′-bipyridine) are synthesized. According to the X-ray diffraction data (CIF file CCDC 986259), the crystal structure of compound I consists of molecules of the mononuclear complex [Sm(2,2′-Bipy)(C₄H₈NCS₂)₃] and solvate molecules CH₂Cl₂ (2 : 1). The coordination polyhedron N₂S₆ of the Sm atom is a distorted tetragonal antiprism. The X-ray diffraction analysis shows that compounds I–V are isostructural. The magnetic properties of compounds I–V are analyzed in the temperature range from 2 to 300 K. At 300 K compounds I and III are photoluminescent in the visible spectral range. The photoluminescence intensity of compound I considerably exceeds that of complex III.     

Synthesis and Crystal Structure of [Cp_2Ln(OC(SEt)NPh )]_2

1 INTRODUCTION The insertion of unsaturated molecules into the lanthanide-ligand bond has attracted considerable attention, because it is a fundamental step for many metal-promoted transformations, in which some va- luable new methods for the formation of carbon- carbon and carbon-heteroatom bonds can be deve- loped and some complexes with novel structures or peculiar characters can be obtained[1~4]. Notably, in contrast to the wide reaction chemistry of organo- lanthanide alkyl (aryl), am…