Synthesis and crystal structure of a novel double 1：11 series arsenotungstate： [Cu^I（phen）2]5H6[Sm（AsW11O39）2]·6H2O

A novel double 1：11 series arsenotungstate, [Cu^I（phen）2]5H6[Sm（AsW11O39）2]·6H2O （phen=1, 10-phenanthroline） was synthesized by the hydrothermal method and characterized by elemental analysis, 1R spectra, and single-crystal X-ray diffraction. The title compound was monoclinic, space group P2 1/c, a=3.75710（2） nm, b=1.39776（8） nm, c=-3.33735（18） nm, β=96.967（10）°, V=17.3969（17） nm^3, Z=4. Single crystal X-ray structural analyses revealed that the dimeric polyanion, [SmAs2W22O78]^1-, consisted of one central Sm^3＋ ion and two tetradentate heteropoly ligands [ASW11O39]^7-. The Sm^3＋ ion and two tetradentate defective [AsW11O39]^7- anions were joined together by the sharing of four oxygen atoms from each heteropoly ligand. The bond valence sum （BVS） calculations of the title compound suggested that all four Cu atoms were in the ＋1 oxidation sate.     

Synthesis and crystal structure of a 1D chainlike rare earth coordinated tungstogermenate： [（CH3）4N]1.50H3.50[Gd（GeW11O39）（H2O）2]·2.5H2O

A 1D zigzag polyoxometalate [(CH3)4N]1.50H3.50[Gd(GeW11O39)(H2O)2]·2.5H2O(1) was synthesized by reaction of the monova-cant polyanion [α-GeW11O39]8- with Gd3+ ions in aqueous solution and characterized by IR, UV spectra, ICP, and X-ray crystallography. X-ray single-crystal structural analysis indicated that the title compound crystallized in a monoclinic lattice, C2/c space group with α=2.8201(5), b=2.2885(3), c=2.4033(4) nm,β=123.875 (2)°, V=12.878(4) nm3, Z=8, R1=0.0623, wR2=0.1287. The solid-state structure of the title compound displayed an infinite one-dimensional arrangement built up of [α-GeW11O39]8- polyanions connected by GdⅢ cations.     

Synthesis and crystal structure of（C5Me4SiMe3）[（^iPrN）2CCH2SiMe3]2Y

Reaction of (C5Me4SiMe3)Y(CH2SiMe)2(THF) with two equivalents of iPrN=C=NiPr in hexane at room temperature afforded a mixed-ligand yttrium complex (C5Me4SiMe3)[(iPrN)2CCH2SiMe3]2Y. X-ray diffraction revealed that the center metal was nine-coordinated by one cyclopentadienyl ring and two amidinate ligands, and adopted a four-legged piano stool geometry.     

Syntheses,characterization, and luminescence of two lanthanide complexes [Ln2（acetate）6（HeO）4]·4H2O （Ln=Tb（1）, Sm（2））

Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.     

Synthesis,crystal structure,and fluorescence of two dimeric europium（Ⅲ） complexes with 2-（trifluoromethyl）benzoate

Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.     

Synthesis and Structure of a Polymeric Complex [Ce（bphsb）2（NO3）3]n

Polymeric cerium nitrate complex with 1,4-bis (phenylsulfinyl) butane (bphsb) [Ce(bphsb)2(NO3)3]n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb and cerium( Ⅲ ) ion form a polymeric double-bridge chain complex involving 18-membered macrometallocycles. Each cerium ion is coordinated by ten 0 atoms in a distorted 4,4-bicapped square antiprism. In the complex the disulfoxide ligand acts as bis-monodentate O-ligand bridging metal centers.     

两种丙烯酸盐[Ln2(CH2CHCOO)6·3H2O]·3H2O(Ln=Ce;Nd)的单晶结构

采用X射线单晶衍射法,解析了[Ln2(CH:CHCOO)6·3H2O]·3H2O(Ln=Ce;Nd)的结构.结果表明标题化合物属同构:属单斜晶系(空间群P2(1)/c);[Ce2(CH2CHCOO)6·3H2O]·3H2O晶胞参数α=1.02099(13)nm,b=1.52294(19)nm,c=2.0325(3)nin,/3=100.838(2)°,V=3.1039(7)nm3;[Nd2(CH2CHCOO)6·3H2O]·3H2O晶胞参数α=1.01978(8)nm,6=1.50979(12)nm,c=2.02712(16)nm,β=100.881(1)°,V=3.0650(4)nm3.化合物不对称结构单元中含有两个独立的稀土中心离子,分别处九、十配位环境中.两个稀土离子由两个独立的丙烯酸μ2-氧桥联形成左手和右手螺旋链.螺旋链通过链间的水分子形成氢键网络,堆垛成三维结构.     

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6(COO)6](H2O)6} and {Ho2[C6(COO)6](H2O)6}

Two novel 3-D coordination compounds, Nd2[C6(COO)6](H2O)6(1)and Ho2[C6(COO)6](H2O)6(2), were hydrothermally synthe-sized from mellitic acid and neodymium perchlorate (or holmium perchlorate) in the alkaline aqueous solution and characterized with ele-mental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the ortho-rhombic system, space group Pnnm, with a=1.3531 (4) nm, b=0.6687 (2) nm, c=1.0224(3) nm, V=0.92523(5) nm3, Z=4, D=2.630 g/cm3, F(000)=696.0, Goof=1.052. Final R indices [I 2Σ(I)]: R1=0.0195, wR2=0.0382 for 1; a=1.3411(2) nm, b=0.6586(1) nm, c=1.0116(2) nm, V=0.8935(3) nm3, Z=4, D=2.877 g/cm3, F(000)=724.0, Goof=1.061. Final R indices [I 2Σ(I)]: R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.     

Synthesis and Crystal Structure of A Bimetallic Terbium Complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3 （THF）3

The reaction of 2, 6-^iPr2CbH3NHSiMe3 with Tb（CH2SiMe3）3（THF）2 in benzene at room temperature afforded a binuclear terbium complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3（THF）3. X-ray diffraction revealed that Tb atoms were bridged by three methylene units. One Tb atom was six-coordinated by two nitrogen atoms, three methylene carbons, and one THF molecule, while the other Tb atom was six-coordinated by one nitrogen atom, three methylene carbons, and two THF molecules. Both Tb atoms adopted a distorted trigonal prism geometry.     

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd_2[C_6(COO)_6](H_2O)_6} and {Ho_2[C_6(COO)_6](H_2O)_6}

Two novel 3-D coordination compounds, Nd2[C6(COO)6](H2O)6 (1) and Ho2[C6(COO)6](H2O)6 (2), were hydrothermally synthe-sized from mellitic acid and neodymium perchlorate (or holmium perchlorate) in the alkaline aqueous solution and characterized with ele-mental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the ortho-rhombic system, space group Pnnm, with a=1.3531 (4) nm, b=0.6687 (2) nm, c=1.0224(3) nm, V=0.92523(5) nm3, Z=4, D=2.630 g/cm3, F(000)=696.0, Goof=1.052. Final R indices [I >2Σ(I)]: R1=0.0195, wR2=0.0382 for 1; a=1.3411(2) nm, b=0.6586(1) nm, c=1.0116(2) nm, V=0.8935(3) nm3, Z=4, D=2.877 g/cm3, F(000)=724.0, Goof=1.061. Final R indices [I >2Σ(I)]: R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.     

Hydrothermal Synthesis of RbLn2F7 and VUV Spectroscopy of RbLn2 F7 ：Eu^3＋（Ln=Gd, Y）

RbLn2F7（Ln = Gd, Y, Er, Yb and Lu）, crystallized in the hexagonal RbEr2F7 structure type, is synthesized by a hydrothermal method. The excitation spectra of Eu^3 ＋ -doped RbGd （Y）2F7 suggest that the oxygen content is very low in the samples obtained by hydrothermal synthesis. Only the f-f transitions of Gd^3＋ ions are observed in the excitation spectrum of RbGd2F7：Eu^3＋ （0.5mol%）, while those of Eu^3＋ ions do not appear. When the Gd^3＋ ions are excited, the absorbed energy is transferred efficiently from Gd^3＋ to Eu^3＋ . The spectra show that the doped Eu^3＋ ions are located in non-centrosymmetric sites in hexagonal RbLn2F7.     

Structural and Electrical Properties of Layered Pervoskite Manganites Nd2-2x Sr1＋2x Mn2O7 （x=0.25, 0.3, 0.4）

Tetragonally layered perovskite manganites of Nd2-2xSr1＋2xMn2O7（x =0.25, 0.3, 0.4） were fabricated by using solid-state reaction technique. Structural characterization of the compounds was investigated by X-ray diffraction （XRD） and FT-IR absorption spectra. The XRD patterns revealed that all the samples were single phase. X-ray photoemission spectroscopy （XPS） was used to investigate their electronic structures. It was found that manganese was in mixed states of Mn^3＋ and Mn^4＋ whereas lattice oxygen and chemical absorbed oxygen were existed in all the samples. The high temperature electrical properties of Nd2-2xSr1＋2xMn2O7 （x = 0.3, 0.4） were measured by standard four-probe technique. The results showed that both compounds had semi-conductivity behavior in the temperature range of 300 - 1073 K, and the electrical conduction was dominated by thermally activated behavior above 500 K.     

Flux and concentration effect on Eu^3＋ doped Gd2（MoO4）3 phosphor

A novel red emitting phosphor Gd2（MoO4）3：Eu^3＋ was prepared by solid reaction, using Gd2O3, Eu2O3 and WO3 as starting matedals and NH4F as flux. The effects of flux content and Eu^3＋ concentration on the crystal structure, morphology and luminescent properties were investigated using XRD, SEM and fluorescent spectrum measurement. The XRD patterns showed that the resultants had the monoclinic structure. With the increase in flux amount, their crystallization significantly improved. The SEM images indicated that the mean size of the phosphor particles was around 2 μm, and agglomeration of the phosphor particles appeared while introducing higher flux amount. The excitation spectra exhibited more intense f-f transitions originating from ground state 7^F0 to upper states 5^L6 and 5^D2 than the charge transfer band. The concentration quenching of Eu^3＋ emission indicated that energy transfer from Eu^3＋ to molybdate host existed even at lower Eu^3＋ concentration.     

Emission Characteristics of PVK Doped TbY（o-MBA）6（phen）2 Systems

Since the pioneering work of Tang and VanSlykeon organic light emitting diodes(OLEDs)in1987,OLEDs have been particularlyinterestedin because oftheir potential applications in next-generationflat-pan-el displays and large-area flexible displays[1~3].Rareearth complex materials have been widely used incathodoluminescent display phosphor screens,lasersand lamps because their photoluminescence PL ex-hibits high quantumefficiencies and very sharp spec-tral bands.Inthe1990s,Kido et al[4~6]first…     

Thermochemical Study on Ternary Solid Complex of La(Gly)2 (Ala)3 Cl3 ·2H2O (s)

The complex of lanthanum chloride with Glycine and Alanine, La(Gly)₂(Ala)₃Cl₃ · 2H₂O, was synthesized and characterized by IR, elementary analysis, thermogravimetric analysis, and chemical analysis. The dissolution enthalpies of LaCl₃ · 7H₂O(s), 2Gly(s) + 3Ala(s) and La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) were determined in 2 mol · L⁻¹ HCl by a solution-reaction isoperibol calorimeter. By designing a thermochemical cycle in terms of Hess' Law and through calculation, the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained: Δ_rH^θ_m(298.15 K) = (29.652 ± 0.504) kJ · mol⁻¹, and the standard enthalpy of formation of La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) Δ_fH^θ_m[La(Gly)₂ (Ala)₃Cl₃ · 2H₂O, s, 298.15 K] = −4467.6 ± 8.3 kJ · mol⁻¹.     

Crystal structure and infrared spectrum of thallium holmium polyphosphate,TIHo（PO3）4

Crystals of thallium-holmium polyphosphate T1Ho（PO3）4 were grown by flux method technique and characterized by single crystal X-ray diffraction. Structure of T1Ho（PO3）4 was solved for the first time, and it crystallized in the monoclinic P21/n space group with the following unit-cell dimensions： a=1.02225（3） nm, b=0.88536（2） nm, c=1.09541（4） nm, β=105.888（1）°, V=0.95354（5） nm^3 and Z=4. The crystal structure was solved from 2174 independent reflections with final R1（F^2）=0.0442 and Rw（F^2）=0.0861 refined with 164 parameters. The atomic arrangement could be described as a long chain polyphosphate organization. Holmium atoms had eightfold coordination. The structure of T1Ho（PO3）4 consisted of HoO8 polyhedra sharing oxygen atoms with phosphoric group PO4. Infrared spectrum was investigated at room temperature in the frequencies range, 350--4000 cm^-1, showing some characteristic vibration bands of infinite chain structure of PO4 tetrahedra linked by bridging oxygen.