Synthesis,Structure and Properties of Three-dimensional Gd(Ⅲ),Eu(Ⅲ) Coordination Polymers via in situ Decarboxylation

Two three-dimensional lanthanide(Ⅲ) coordination polymers with the formula [Ln(PYDC)(NA)(H2O)]n [Ln=Gd(1), Eu(2), H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthe- sized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are iso- morphous, they possess the 43·63 topology assembled by Gd3+/Eu3+ and two di...     

Synthesis,Structure and Luminescent Properties of Three 1D Chain Rare Earth Complexes

Three 1 D chain coordination polymers [Ln(pydc)2(H2 O)2]n·n Him(Ln = Dy(1), Gd(2), Sm(3), H2 pydc = pyridine-2,5-dicarboxylic acid, Im = imidazole), were solvothermally synthesized by the reaction of pyridine-2,5-dicarboxylic acid(H2 pydc), Ln(Ⅲ) salts and imidazole. They have been characterized by X-ray single-crystal diffraction, IR spectra, TGA analysis and elemental analysis. Structural analyses revealed that complexes 1～3 have similar 1 D chain structures and belong to P1 space group. It is noteworthy that complexes 1～3 exhibited excellent thermal stability and no weightlessness below 117 ℃. Meanwhile, 1 and 3 show characteristic fluorescence of corresponding lanthanide metal ions in solid state at room temperature.     

1D Lanthanide Coordination Polymers Based on 3-（Pyridin-4,yl）benzoic Acid： Syntheses, Structures and Luminescent Properties

Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(H2O)2· H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoclinic system, space group P1. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.     

Syntheses and Properties of K_17[Ln(CuW_11O_39)_2]·xH_2O

Heteropoly-complexes K17[Ln(CuW11O39)2].xH2O(Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy) were prepared. The properties of the products were investigated by ion-exchange, conductometric titration, IR, UV and X-ray powder diffraction. The results show that the structure of the products is similar to that of U(a-Ge11O39)2 and consistent with the model proposed by Peacock.     

Syntheses and Crystal Structures of Lanthanide Complexes of New 15-Membered Macrocyclic Ligands with Three Pendant Acetato Groups

Two new 15-memhored fimctionalized macrocycles, dioxo-polyazacydoalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhy-dride (DTPA = diethylenetrlamlnepentaacetic acid ) with 1,2-di-amlnopropane, ( 15-DTPA-1, 2-pn), or 1, 2-diaminocydohex-ane, (15-DTPA-1,2-cy). Their lanthanide complexes [ Ln ( 15-DTPA-1,2-pn)(H2O)]2[Ln= Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H2O)]2[Ln= Eu (3), Gd (4)] were also pre-pared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state;each metal ion is nine-coordinated in a distorted tricapped-trig-onal prism. In complex 4, the coexistence of two diastereoiso-meric molecules in the crystal lattice was observed.     

Synthesis, Crystal Structure and Magnetic Properties of a Sandwich-type Polyoxometalate [H2N（CH2CH2）20]10[Mn2（AsVMo9Oa3）2]·12H2O

A new heteropolymolybdoarsenate [H2N(CH2CH2)2O]10[Mn2(AsVMo9O33)2]·12H2O(1) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. The crystal is made up of sandwich-type [Mn2(AsVMo9O33)2]10- anions, [H2N(CH2CH2)2O]+ cations and H2O molecules of crystallization. The magnetic properties of 1 have been studied by measuring its magnetic susceptibility in the temperature range of 2.0-300.0 K, indicating the existence of antiferromagnetic interactions.     

Synthesis,structure and catalytic activity of complexes [Ln(EDBP)_2(DME)Na(DME)_3](Ln=Er,Yb,Sm) for ring-opening polymerization of ε-caprolactone

Discrete ion-pair complexes [Ln(EDBP)2(DME)Na(DME)3] [Ln=Er (1), Yb (2), Sm (3)] have been synthesized by the reaction between sodium salt of 2,2'-ethylidene-bis(4,6-di-tert-butylphenol)(EDBPH2) and Ln(BH4)3·3THF (Ln=Er, Yb, Sm) followed by centrifugation and recrystalization. The complexes were characterized by elemental analysis and FT-IR, and the bonding model of these compounds was confirmed by X-ray single crystal diffraction for complex 1. It was found that four O atoms in two biphenol ligands as well...     

Synthesis and characterization of novel heteronuclear complexes of Ln(Ⅲ)-Cu(Ⅱ) with non-cyclic polyether Schiff base

Nine novel heteronuclear complexes of Ln(Ⅲ)-Cu(Ⅱ) with salicylidene tetraethvlcne glycol diamine (SALTTA) have been synthesized and characterized.They have the general formulae [LnCu2(SALTTA)2(NO3)3](NO3)4 3H2O (Ln=La,Pr.Nd,Srn) and [LnCu3(SALTTA)3(NO3)5]-(NO3)4-4H2O (Ln=Gd,Tb,Er,Yb,Y).The IR spectra show that vc=N in the Ln(Ⅲ)-Cu(Ⅱ) het-eronuclear complexes are splitted up into two peaks with a far distance.It has been confirmed that oxygen atoms in oxyethylene of the ligand are not all coordinated to the central metal ions by both IR and NMR methods.     

Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ) Complexes Based on Carboxyl Derivatives of 1 ,10-Phenanthroline

Three lanthanide(III) complexes [Ln(4-NCP)(1,4-BDC)]n·xn H2O(Ln = Pr(1), Sm(2), Nd(3). 4-HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid) have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4~(12)·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.     

Syntheses and Crystal Structures of Five SrⅡ-LnⅢ （Ln = N小 Pr,Er） Heterometallic Coordination Polymers

Five novel SrⅡ-LnⅢ heterometallic coordination polymers based on pyridine-2,6- dicarboxylic acid （H2pda） and imidazole （im）, namely, [LnSr（pda）3（H2O）5]-Him·C2H5OH·3H2O （Ln = Nd （1）; Pr （2））, [Ln2Sr（pda）6（H2O）5]-4Him·C2H5OH·5H2O （Ln = Nd （3）; Pr （4））, and [ErSr（pda）3（H2O）4].Him-3.5H2O （5）, have been prepared and structurally characterized. X-ray crystallographic analyses revealed that these complexes display three varieties of l-D chain structures. Several types of hydrogen bonding interactions are found for 1-5, which connect the 1 -D chain structures to form 2-D suoramolecular networks.     

(C26H40N2O4)[Ln(NO3)5H2O]的合成及其铕缔合物的晶体结构

合成了4个新型的稀土化合物(C₂₆H₄₀N₂O₄)[Ln(NO₃)₅H₂O](Ln=Pr,Nd,Sm,Eu),采用元素分析和红外光谱表征,用四圆衍射仪测定了其中(C₂₆H₄₀N₂O₄)[Eu(NO₃)₅H₂O]的晶体结构,属三斜晶系,P1空间群,晶胞参数:α=0.9100(4)nm,b=1.3560(3)nm,c=1.6463(4)nm;α=68.62(2)°,β=74.84(3)°,γ=87.50(2)°;Z=2.中心铕离子由5个硝酸根的10个氧原子和1个水分子中的氧原子配位,配位数是11.1,7,10,16-四氧-4,13-二氮杂-N,N'-二苄基环十八烷(N,N'-二苄基穴醚(2,2))未参与配位.     

Two New Piperazine Templated Lanthanide Sulfates with 2D Corrugated Layered Crystal Structures

Two new piperazine templated lanthanide sulfates (C₄N₂H₁₂)_1.5[Ln(SO₄)₃(H₂O)]·H₂O[Ln=Gd(1), Tb(2)] have been synthesized solvothermally and structurally characterized by single crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Single crystal X-ray diffraction reveals that both compounds 1 and 2 crystallized in the monoclinic crystal system, with space group P2₁/c and cell dimensions: a=0.64468(19) nm, b=2.9979(9) nm, c=0.9818(3) nm, β=101.271(4)°, V=1.8608(10) nm³, Z=4 for compound 1; a=0.64259(19) nm, b=3.0010(9) nm, c=0.9812(3) nm, β=101.229(4)°, V=1.8560(10) nm³, Z=4 for compound 2. Compounds 1 and 2 are isomorphous and have similar 2D corrugated inorganic frameworks fabricated via the connection of single chains and S2O₄ groups, while fully protonated piperazine cations and water molecules are located between the inorganic layers. The solid state luminescent properties of compound 2 were investigated and it displayed a typical luminescent property of Tb³⁺ with excitation wavelength at 371 nm.     

镧系元素杂多钨砷酸盐的合成与性质研究

本文报道了镧系元素的杂多钨砷酸钾K₁₁[Ln(AsW₁₁O₃₉)₂]·xH₂O(Ln:La、Ce、Pr、Nd、Sm)的合成方法和X-射线粉末衍射、红外及拉曼光谱、X-光电子能谱及有效磁矩的研究结果。     

Preparation and characterization of single crystals[Ln(TBPO)4(NO3)2]NTf2 (Ln=Eu,Gd)

Two single crystals[Ln(TBPO)₄(NO₃)₂]NTf₂ (Ln=Eu, Gd) were prepared and characterized by element analysis, single crystal X-ray diffraction, PXRD, FT-IR, TGA and fluorescence spectroscopy. The two compounds have similar coordinate structures, in which the central metal ion is coordinated by four TBPO (Tri-n-butylphosphine oxide) molecules and two bidentate nitrates, while NTf₂^-(bis(trifluor-(bis(trifluoromethylsulfonyl) imide anion) acts as the counter anion. The packing modes of the two crystals are same. The two single crystals are the focus on 8-coordinate tetra-TRPO complexes (TRPO is Trialkyphosphine oxides).     

Novel One-dimensional Cyano-bridged Chain Molecular-based Magnet[Ln(DMF)4(H2O)2Mn(CN)6·H2O]n:Crystal Structure,Long-range Magnetic Ordering,High Tc and Strong Coercive Behavior

There has been great interest in the study of the magnetic properties of molecular-based compounds^[1,2]. In the present work, we employed N,N-dimethylformide (DMF) as a hybrid ligand to synthesize a new family of cyano-bridged complexes contain rare earth and Manganese:[Ln(DMF)₄(H₂O)₂Mn(CN)₆·H₂O]_n (abbreviated as LnMn, Ln=Sm, Eu, Gd, Tb, Dy, Er) and the crystal data of former three complexes has been obtained, which display a remarkable variety of magnetochemical behavior and a rich structural chemistry.     

系列Ln(Ⅲ)配聚物的合成、结构及近红外发光性能

通过水热反应合成5种结构新颖的配聚物:{[Ln_2(1,3-bdc)_3(H_2O)_4](DMF(H_2O}_n[Ln=Pr(1),Nd(2),Gd(3)]和{[Ln_4(1,3-bdc)_6(H_2O)_4(DMF)](DMF(2H_2O}_n[Ln=Er(4),Ho(5)](1,3-bdc:间苯二甲酸,DMF:N,N-二甲基酰胺)。通过单晶X射线衍射、红外光谱、紫外-可见-近红外(UV-Vis-NIR)光谱、荧光光谱等技术手段对产物的结构和性能进行了表征。结果表明,配聚物1~3是同构的,属单斜晶系,P2(1)/n空间群;配聚物4、5是同构的,属三斜晶系,P-1空间群。在晶体中,间苯二甲酸根采用多样的配位模式,使配聚物呈现多维的结构。除配聚物4,其余均呈现Ln(Ⅲ)的特征NIR发光,并与其UV-Vis-NIR吸收光谱相关联。     

Synthesis and X-ray crystal structures of bis(bis(μ2-2-aminoethanolato–N,O,O)–cobalt(III))–cobalt(II) hydrate, tris(biscyclohexylammonium)μ-hydroxo–bis(μ2-nitro–N,O)–hexanitro–dicobaltate(III) and biscyclohexylammonium nitrate(III)

Two new cobalt complexes: Co₃(NO₂)₄(NH₂CH₂CH₂O)₄·H₂O (1) and (NH₂(C₆H₁₁)₂)₃[Co₂(NO₂)₈OH]·3H₂O (2) and the compound (NH₂(C₆H₁₁)₂)NO₂ (3) were synthesised and their structures have been determined using single-crystal X-ray diffraction. Compound 1 consists of two centrosymmetrical trinuclear complexes and a water molecule of crystallization. Ligands coordinated to Co atoms are nitro and aminoethanolato groups. Structure 2 is built up of biscyclohexylammonium cations, dinuclear anions with hydroxo and nitro groups coordinated to Co atoms and water molecules. The coordination of Co atoms in both structures is roughly octahedral.     

11-钨硼酸钾的结构和振动光谱研究

标题化合物K₈H(BW₁₁O₃₉)·13H₂O属立方晶系,空间群P43m,a=10.710(1)Å,V=1228.58ų,Z=1;D_O=4.39g·cm^-3,D_c=4.42g·cm^-3。(BW₁₁O₃₉^9-离子属于不饱和α-Keggin型结构,B原子位于O₂四面体的中心。测定并研究了化合物的IR和Raman光谱性质。     

High-pressure,High-temperature Synthesis and Properties of the Monoclinic Phase of Y2O3

The monoclinic phase of Y₂O₃(B-RES) has been synthesized using a Kawai-type multi-anvil apparatus under 20 GPa at 1800 ℃. Samples of the cubic Y₂O₃(C-RES) and monoclinic Y₂O₃ phases were characterized by synchrotron radiation X-ray diffraction, X-ray absorption near edge structure and Raman spectroscopy. Crystal structures of the cubic and monoclinic phases have been examined using Rietveld refinement of the X-ray diffraction data. The cubic-to-monoclinic transition of Y₂O₃ was reconstructive and irreversible. The X-ray diffraction results were further confirmed by simulation of the X-ray absorption spectra.     

Preparation of Nanoparticulate [PMo11Cu(H2O)O39]5--n-C18H37NH2 Film Using Langmuir-BIodgett Method

Nanoparticulate [PMo₁₁Cu(H₂O)O₃₉]^5--(PCuMo₁₁)-n-C₁₈H₃₇NH₂ composite monolayer can be formed at the air-liquid interface using nanoparticulate PCuMo₁₁ as the subphase. The area extrapolated to π=0 is 0.27 nm² per hydrocarbon chain of the monolayer. The collapse pressure is about 3.5×10^-1 N. The composite monolayer was deposited on the solid substrate using the LB technique. The XPS characterization of the composite monolayer showed that in the film the directional alignment of PCuMo₁₁, molecules was in the direction of Cu atoms close to the amino groups of the octadecylamine moleculos.