Synthesis and Characterization of a Novel Compound SnDy2O4

In recent years, the research on rare earth became a focus, and a lot of rare earth complex compounds with AB2O4 stoichiometry were prepared1-3. The compound SnDy2O4 is expected to spinel-type phase while it exhibits a new structure type. SnDy2O4 was prepared by the thermal decomposition of the oxalate precursor that was prepared by rheological phase reaction method. SnO(AR), Dy2O3(99.9%) and H2C2O4·2H2O are ground in molar ratio 1:1:4.1, and placed into the reaction apparatus. …     

[Cu(TO)2(H2O)4](PA)2的制备、结构表征和热分解机理研究

[Cu（TO）2（H2O）4]（PA）2 was prepared by the reaction of aqueous 1,2,4-triazol-5-one （TO） solution with the solution of copper picrate Cu（PA）2 and characterized by elemental analysis, FT IR and X-ray powder diffraction analysis. The title complex has been studied by means of TG-DTG and DSC under conditions of linear temperature increase. The thermal decomposition residues were examined by FT IR analysis. Thermal decomposition mechanism of the title complex was proposed. In the temperature range of 30-680 ℃, the thermal decomposition process was composed of four major stages. The first stage was an endothermic process with the loss of four coordination water molecules. Since the dehydration product was unstable, when it was heated, it would be decomposed much more easily. The second stage was composed of an acute endothermic process and a continued strong exothermic process and the main decomposed residues were CuCO3, Cu（NCO）2 and polymers during this stage. The third stage was a sharp exothermic process, which resulted from the decomposition of the polymer. After the forth stage, the final decomposed residues were certainly copper oxide. The Arrhenius parameters have been also studied on the dehydration process and the first-step exothermic decomposition of [Cu（TO）2（H2O）4]（PA）2 using Kissinger＇s method and Ozawa-Doyle＇s method. The results using both methods were consistent with each other. The Arrhenius equation can be expressed as in k=24.0-179.8 × 10^3/RT for the dehydration process and in k= 16.7-206.0 × 10^3/RT for the first-step exothermic decomposition, on the basis of the average of Ea and In A through the two methods.     

三元稀土配合物RE(NTA)2AA的合成、共聚反应性及荧光性能研究

Four new ternary rare earth complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺， Tb³⁺， Dy³⁺) have been synthesized by the reaction of rare earth chloride(RECl₃·6H₂O) with Acrylic Acid (HAA) and 4，4，4-trifluoro-1-(3-pyridyl)-1，3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺) with methyl methacrylate (MMA) has been studied by 2， 2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2，2′-bipyridine(bipy) into copolymer Eu(NTA)₂AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu， Sm complexes and Eu copolymer can efficiently emit fluorescence， but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.     

STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(Ⅳ)SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 4''''-BROMO-5''''-NITROBENZO-15-CROWN-5

Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)withUivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0,RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char-acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powderdiffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows thatcoordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

Synthesis and Characterization of Dinuclear Rare Earth Complexes Bearing N-heterocyclic Olefin Moieties

The oxygen-bridged dinuclear rare earth complexes(Ln=Nd(1),Y(2))bearing N-heterocyclic olefin moieties were synthesized by treating the imidazolidinium salt[SIMes-H]Br with potassium amide and rare earth bis(trimethylsilyl)amides.Complex 1 was characterized by X-ray diffraction analysis and complex 2 was characterized by 1H NMR spectroscopy.Both complexes were characterized by elemental analysis.Crystal data of complex 1:C74H138O2N8Si8Nd2,Mr=1685.12,orthorhombic,space group Pbca,a=25.1105(7),b=11.9188(2),c=29.6151(7)?,V=8863.4(4)?^3,Z=4,Dc=1.263 g·cm^-3,μ=1.311 mm^-1,F(000)=3544,the final R=0.0418 and wR=0.0770 for all data.The ring-opening of tetrahydrofuran molecule was proven,the possible mechanism for the formation of N-heterocyclic olefin(NHO)-rare earth complexes was speculated and the electronic and steric properties of SIMes and rare earth amides were discussed.This work provides a better understanding of N-heterocyclic carbene rare earth chemistry.     

Synthesis and Structure of Ba3La2（BO3）4 Crystal

1 INTRODUCTION At present the researches on more efficient solid-state laser materials become more important for the rapid development of diode-laser pumped solid-state laser. More researches have been devoted to the double borate compounds RX3(BO3)4 (R = Y, La, Gd and X = Y, Al, Sc), some of which exhibit good chemical and physical properties[1～10]. The rare earth and alkali-halide double borates M3Ln2(BO3)4 (M = Ca, Sr, Ba and Ln = LaLu and Y) were reported in literatures[11…     

Studies on synthesis and kinetics of thermodecomposition of the nickel(Ⅱ) compounds with Schiff base derived from amino acids

Monoaqua salicylaldehyde-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp1) and monoaqua o-vanillin-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp2) were synthesized. The composition and structures of these two compounds were analyzed. Their thermal stability and non-isothermal kinetics were also investigated by use of TG and DTG curves. The possible reaction mechanisms in their first steps of thermal decomposition reactions were deduced by means of integral and differential methods. Thermodecomposition kinetic equations of the compounds are as follows:Cp1: da/At = A . exp(-E/RT) . 3/2(1 - a)4/3 . [1/(1 - a)1/3 -1]-1 Cp2 : da/At = A . exp(-E/RT) . (1 - a)     

Thermal Behavior and Decomposition Kinetics of the Complexes of CuX2 （X=NO3, Br, CI and CIO4） with 3,3＇-Dimethyl-1 -（1 H-1,2,4-triazol-1-yl）-2-butanone

The thermal behaviors of the complexes of Cu(DMTZB)4X2 (DMTZB=3,3‘-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, X=NO3 or ClO4) and Cu(DMTZB)2 X2 (X=Br or Cl) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC, EDS and elemental analysis techniques. The resuits showed that their decomposition proceeded in three different ways mainly depending on the anions in the molecules. The heat effect associated with the decomposition step of DMTZB molecules was also different. The decomposition mechanisms and the kinetic parameters of DMTZB were determined and calculated by jointly using four methods, which showed that its pyrolysis was controlled by D3 mechanism but with different activation energies and pre-exponential factors for different complexes.     

Low-temperature heat capacities and thermodynamic properties of rare-earth triisothiocyanate hydrates (Ⅲ)——Sm(NCS)_3·6H_2O,Gd(NCS)_3·6H_2O,Yb(NCS)_3·6H_2O and Y(NCS)_3·6H_2O

The heat capacities of four RE isothiocyanate hydrates,Sm( NCS)3 6H2O,Gd( NCS)3 6H2O,Yb(NCS)3 6H2O and Y( NCS)3 6H2O,have been measured from 13 to 300 K with a fully-automated adiabatic calorimeter No obvious thermal anomaly was observed for the above-mentioned compounds in the experimental tem-peiatnre ranges.The polynomial equations for calculating the heat capacities of the four compounds in the range of 13-300K were obtained by the least-squares fitting based on the experimental Cp data.The Cp values below 13 K were estimated by using the Debye-Einstem heat capacity functions.The standard molar thermodynamic functions were calculated from 0 to 300 K.Gibbs energies of formation were also calculated.     

高锰酸稀土化合物的制备及性质

把CCl4中的Mn2O7加到稀土氧化物中制备了稀土高锰酸盐. 并测定了它们的化学组成, 研究了它们的红外光谱, 摩尔电导率, X射线粉末衍射及热谱性质试验了高锰酸镧对苯甲醇的氧化能力, 表明比高锰酸钾有更强的氮化能力.     

稀土苯甲酸盐的合成及热分解反应机制

由水热法合成了稀土苯甲酸盐配合物Ｌｎ（Ｃ６Ｈ５ＣＯＯ）３（Ｌｎ＝Ｌａ,Ｎｄ,Ｓｍ,Ｅｕ、Ｇｄ、Ｄｙ、Ｅｒ）。用元素分析、ＩＲ、Ｘ射线粉末衍射表征了该系列配合物。它们都为层状结构,属单斜晶系。用ＴＧ、ＤＴＡ、ＩＲ、色谱－质谱联用仪研究了它们的热分解机制。在氮气氛下,热分解分两步进行：先分解生成二碳酸一氧盐和有机化合物;而后二碳酸一盐进一步分解生成稀土氧化物和二氧化碳。第二步中生成的有机化合物成分比较     

硼合多羟基醇希土配合物的合成与性质及其配位作用的研究

本文合成了硼合甘油希土和硼合葡萄糖希土二类共八个配合物。用化学分析、红外光谱、紫外光谱及热谱确定其组成为:RE(BO_2·C_3H_8O_3)_3·nCH_3OH和RE(BO_2·C_6H_(12)O_6)_3·3H_2O(RE=Nd、Gd、Y、Yb)。摩尔电导测定表明这两类化合物均为中性配合物。红外光谱显示出硼与多羟基醇之间以硼氧四面体形式结合。本文还通过电位滴定法讨论了希土与硼合多羟基醇之间的配位作用。     

RECl3与丝氨酸配合行为的研究

依据相平衡结果，于水中合成了ＲＥ（Ｓｅｒ）Ｃｌ３．３Ｈ２Ｏ和ＲＥ（Ｓｅｒ）２Ｃｌ３．５Ｈ２Ｏ（ＲＥ＝Ｌａ－Ｎｄ，Ｓｍ－Ｇｄ，Ｄｙ，ｙｂ，Ｙ）等２０种固态配合笺，利用化学分析，摩尔电导，ＩＲ、ＵＶ、ＦＳ、Ｘ射线衍射分析及ＴＧ－ＤＴＧ等手段对配合物进行了表征。     

稀土配合物的研究(Ⅸ)——稀土元素与1,5-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)戊二酮-(1,5)配合物的合成及性质

乙醇-水混合体系中合成了15种新的稀土元素的固态配合物,通过元素分析和化学分析确定了配合物的化学组成为RE_2(BPMPPD)_3·nH_2O和Ce(BPMPPD)_2·6H_2O(BPMPPD为1,5-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)戊二酮-[1,5]),对配合物的荧光光谱等性质进行了研究。     

RE(ClO_4)_3·nH_2O与丙氨酸、咪唑配合物的合成、表征及生物活性

研究了 9种RE(ClO4) 3·nH2 O与Ala(丙氨酸 CH3CHNH2 COOH)及Im(咪唑 )在甲醇中的配位作用。用化学分析、元素分析、IR、UV、FS光谱及X射线粉末衍射对配合物进行了表征。确定了其组成为RE(Ala) 2 Im (ClO4) 3·nH2 O (RE =Ce ,Sm ,n =2 ;RE =Pr ,Nd ,Eu ,Gd ,Tb ,Yb ,n =1)及La(Ala) 3Im(ClO4) 3·3H2 O。并结合1 HNMR及TG DTG进一步研究了新配合物的配位行为及热分解机制。生物活性测定结果表明 ,该类配合物尤其是重稀土配合物具有明显的广谱抑菌作用。     

稀土异硫氰酸盐与二甲基亚砜配合物的合成,性质及热分析研究

合成了15种稀土异硫氰酸盐与二甲基亚砜(DMSO)的配合物,经化学分析和元素分析确定其组成为RE(NCS)_s·mDMSO(RE=La,Ce,Pr,Nd,Sm,Eu,Gd;m=5.RE=Tb,Dy,Ho,Er,Tm,Yb,Lu,Y;m=4).用红外光谱及X射线衍射技术进行了表征.运用TG-DTA-DTG联用技术研究了该系列配合物的热分解过程,求算热重动力学参数发现,第一步热分解阶段的活化能随着中心高子——镧系元素原子序数的依次递增呈现“双峰现象”.     

氨噻肟酸稀土配合物的合成、抗氧化性及抗菌活性的研究

合成了１２种稀土氨噻肟酸（ＨＬ）固体配合物,其通式为ＲＥＬ３（ＲＥ＝Ｌａ,Ｃａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｔｂ,Ｅｒ、Ｔｍ,Ｙｂ,Ｙ）。利用元素分析、红外光谱、核磁共振氢谱、摩尔电导、热分析等测试手段对配合物进行了表征,研究了ＮｄＬ３、ＥｒＬ３配合物在ＤＭＳＯ溶液中电子吸收光谱,计算了电子云伸效应参数β,共价参数　和键合参数ｂ＾１／２,讨论了配合物的共价成键情况,并对其抗氧化及抗菌活性做了研究     

稀土发光配合物的研究Ⅱ.稀土,3-吡啶甲酸,邻菲咯啉三元配合物的合成和荧光性质

合成了１４种稀土元素与３吡啶甲酸（ＨＬ）及邻菲咯啉（Ｐｈｅｎ）的三元配合物,通过元素分析和化学分析确定其化学组成为ＲＥＬ３·Ｐｈｅｎ,并利用ＩＲ、ＵＶ、１ＨＮＭＲ、ＴＧＤＴＡ和Ｘ射线粉末衍射等手段对配合物进行了表征．研究了Ｅｕ（Ⅲ）及Ｔｂ（Ⅲ）配合物的荧光性质．     

水合稀土二氯醋酸盐的合成及热分解研究

合成了La,Ce,Nd,Sm,Eu,Gd二氯醋酸盐,经化学分析,热重法和五氧化二磷真空千燥脱水法确定组成为Ln(CHCl2COO)3.nH2O(n=2,Ln=La,Ce,Nd;n=1.5,Ln=Sm;n=1.25,Ln=Eu;n=1,Ln=Gd),它们均属新水合物.用DTA-TG-DTG并用技术并辅以化学分析和红外光谱技术研究了其热分解机理,实验证明,由室温至600℃范围内,它们均发生三步主要反应:水合盐脱水变为无水盐;无水盐分解为中间产物,Ln2(OH)Cl5.3H2O[Eu盐分解为Eu2(OH)Cl5.2H2O];中间产物进一步分解为LnOCl[Ce盐为CeO2].并观察到无水盐和氯氧化物形成温度皆与原子序数呈现镧系"双一双效应".