稀土(III)三硬脂酸盐LB膜的制备及结构研究

用直接在5×10^-^5mol.dm^-^3稀土(III)氯化物水溶液的液面上铺展稀土(III)三硬脂酸盐(简称LnSt~3)的方法,在疏水光学玻璃片上连续沉积了44层以上的含稀土(III)(La、Nd、Sm、Eu、Tb)硬脂酸盐LB膜,转移比为0.7-0.8。低角度X射线衍射(2θ=0.3-14ⅲ)结果表明,膜的结构为高度有序的层状结构,相邻稀土离子面的间距为4.7-4.8nm。X射线光电子能谱(XPS)证实了五种膜中分别含有La、Nd、Sm、Eu和Tb元素。此外,还对LnSt~3LB膜进行了红外光谱考察,表明在亚相中加入一定浓度的稀土离子能有效地抑止界面上LnSt~3的水解作用,为制备含稀土(III)离子的优质LB膜提供了依据。     

二茂铁丙烯酸稀土配合物的合成与表征

本文用氯化稀土(RECl_3)与二茂铁丙烯酸钠盐(LNa)在无水乙醇中反应,合成了13种新的稀土配合物。由元素分析、红外光谱和热谱分析确定配合物的组成为:(C_5H_5FeC_5H_4CH=CHCOO)_3RE·H_O(RE=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb),配体羧基以双齿对称螯合方式与稀土离子配位。经X射线粉末衍射分析,对其晶体结构进行了初步探讨。     

有生物活性的稀土-腺苷三磷酸系列物的合成及其量子化学理论计算的研究

本文首次报道合成了稀土-腺苷三磷酸固态配合物RE(III)-ATP)RE=Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu)。运用红外、激光raman、热分析、紫外、顺磁、X射线衍射、元素分析、配位滴定等技术测定了上述配合物的化学组成和分子结构, 其分子式用通式表为[RE(III)(HATP)(H2O)4]。采用量子化学INDO方法计算了系列物的电子结构, 依据计算结果讨论了生物化学中高能磷酸键的本质。     

双长链烷基稀土杂多酸化合物LB膜的制备、结构及性质研究

制备了三种新型双窗长链烷基稀土杂多酸化合物langmuir和langmuir-blodgett膜：DODA/Ln(PW~1~1)~2(Ln=La,Sm,Eu)。用π-A等温线,IR,UV,小角X射线衍射,荧光光谱,光电压谱对其进行了表征。结果表明：它们在空气-水界面有良好的成膜性能,这些单层在表面压为零时,表观单分子占有面积为0.45～0.50nm^2。LB膜有良好的层间有序性,稀土杂多酸阴离子是作为一无机层夹在两个双长链烷基层之间。DODA/Ln(PW)~1~1)~2LB膜具有Sm,Eu的特征荧光,其光电压谱亦有较强的光电响应。     

双长链烷基稀土杂多酸化合物LB膜的制备、结构及性质研究

制备了三种新型双窗长链烷基稀土杂多酸化合物langmuir和langmuir-blodgett膜：DODA/Ln(PW~1~1)~2(Ln=La,Sm,Eu)。用π-A等温线,IR,UV,小角X射线衍射,荧光光谱,光电压谱对其进行了表征。结果表明：它们在空气-水界面有良好的成膜性能,这些单层在表面压为零时,表观单分子占有面积为0.45～0.50nm^2。LB膜有良好的层间有序性,稀土杂多酸阴离子是作为一无机层夹在两个双长链烷基层之间。DODA/Ln(PW)~1~1)~2LB膜具有Sm,Eu的特征荧光,其光电压谱亦有较强的光电响应。     

新型长余辉发光材料SrMgSi2O6:Eu2+,Ln3+的制备及性质

采用凝胶-燃烧法合成了系列稀土离子掺杂的Sr0.94MgSi2O6:Eu0.022+,Ln0.043+(Ln=La,Ce,Nd,Sm,Gd,Dy)蓝色长余辉发光材料,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光分光光度计等对合成产物进行了分析和表征.结果表明:掺杂了不同稀土离子的SrMgSi2O6:Eu2+,La3+的晶体结构均为网方品系结构;其激发、发射光谱的峰形、峰位基本无变化,激发光谱为一宽带,最大激发峰位于400 nm处,次激发峰佗于415 nm处,发射光谱也为一宽带,最大发射峰位于470 nm附近,是典型的Eu2+的4F5d_4f跃迁导致的,不同之处在于其激发光谱、发射光谱强度及余辉性质有所差别,其中Dy3+是最理想的共掺杂稀土离子,Sr0.94MgSi2O6:Eu0.022+Dy0.043+的余辉时间最长,可达4 h;而Sm3+最差,Sr0.94MgSi2O6:Eu0.022+,Sm0.043+的余辉亮度最低,余辉时间最短.     

稀土季铵盐络合物的研究(Ⅲ)——硝酸合稀土酸四丁基季铵盐粉末衍射数据

借助于X射线衍射仪的慢扫描和最小二乘法修正,得到了[(C_4H_9)_4N]_xLn[NO_3)_y系列14个络合物的晶胞参数和粉末衍射数据当Ln=La、Pr、Nd时,x=3,y=6;Ln=Sm、Eu、Gd、Tb、Dy、Ho、Er,Tm、Yb、Lu、Y时,x=2,y=5)。发现,随稀土离子原子序数的增大,络合物的晶胞体积减小和密度增大。     

RE（Ⅲ）—ADP,RE（Ⅲ）—AMP配合物的合成及物性研究

首次合成了具有生物活性的系列配合物RE(Ⅲ)-ADP(稀土-腺苷二磷酸)和RE(Ⅲ)-AMP(稀土-腺苷-磷酸)(RE=Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu),根据红外、紫外、荧光、X射线衍射、元素分析、络合滴定等分析结果,研究了[RE(Ⅲ)(ADP)(H_2O)_3]和[RE(Ⅲ)(AMP)_2(H_2O)_4]H两个系列配合物的化学组成和性质。     

氯化稀土与丙氨酸配合行为的研究

用半微量相平衡方法研究了SmCl~3-Ala-H~2O三元体系在25℃时的溶解度。结果表明体系中形成了两种配合物: Sm(Ala)~2Cl~3.3H~2O和Sm(Ala)~3Cl~3.3H~2O,合成了RE(Ala)~3Cl~3.3H~2O(RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy),RE(Ala)~2Cl~3.nH~2O(RE=La, Ce, Pr, Nd, Sm, n=3; RE=Ho, Yb,Y, n=4)与RE(AlA)Cl~3.6H~2O(RE=Eu, Gd,Tb, Dy, Ho, Yb, Y)二十四种固体配合物, 用化学分析、IR、UV、X射线分析及TG-DTG对配合物进行了表征, 发现了RECl~3与Ala形成配合物的规律性。     

(La1-xREx)2/3Sr1/3MnO3(RE=Y,Sm,Eu,Tb;x=0.1～0.5)的晶体结构及磁性质研究

采用空气中固相反应烧结法制备了一系列钙钛矿结构的(La1-xREx)2/3Sr1/3MnO3(RE=Y,Sm,Eu,Tb;x=0.1～0.5)稀土锰氧化物多晶样品.X射线衍射(XRD)分析表明掺杂RE部分替代La以后,样品的晶体结构为正交结构,空间群为Pbmm.在室温(300K)和液氮温度(77K)下分别测试了样品的磁性质,发现磁性质的改变与RE的掺入量以及RE的离子半径有关.在掺Tb的样品中明显存在巨磁电阻效应,磁场为2 T,温度为300和77 K分别测得(La0.6Tb0.4)2/3Sr1/3MnO3和(La0.7Tb0.3)2/3Sr1/3MnO3的磁电阻(MR)为80%和85%.随着Tb掺杂量的增加,在不同的磁场下,样品电阻-温度关系曲线的峰均向高温方向移动.     

Determination of rare earths and thorium in apatites by thermal and epithermal neutron-activation analysis

A procedure is described for the non-destructive determination of Na, Mn, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu and Th in apatites by thermal and epithermal neutron-activation of independent portions of the material. The method was applied to three apatites with different contents. The precision obtained was better than +/-5% for La, Ce, Sm, Eu, Gd, Tb and Dy and +/-20% for Yb, Nd, Ho, Er and Lu for an apatite with a total rare-earth oxide content of the order of 1%. Determination of Ce, Tb and Yb could only be carried out with thermal neutron-activation analysis, while Gd, Ho and Er could only be determined after irradiation with epithermal neutrons.     

钼和稀土的二乙基二硫代甲酸盐配合物的电化学研究

研究了N,N-二乙基二硫代甲酸根(dtc)作配体的双核配位化合物[Mo(dtc)₄][Ln(dtc)₄](Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho和Er)的氧化还原性质及其在电极过程中的电化学特性.     

Determination of rare earths in rare-earth concentrates by neutron activation analysis

Neutron activation analysis was applied to the determination of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Lu and Th in rare-earth concentrates resulting from minerals. High-resolution gamma-ray spectrometry with a Ge(Li) detector was used for the non-destructive determination, and a single comparator method using Co as flux monitor was applied.     

Synthesis,characterization and tg-dsc study of lanthanide trifluoroacetate-2-azacyclononanone compounds

The synthesis, characterization and tg-dsc study of Ln(tfa)₃?·?3aza where Ln?=?La, Pr, Nd, Sm, Eu, Gd, Tb and Er, tfa?=?trifluoroacetate and aza?=?2-azacyclononanone are reported. The obtained X-ray powder diffraction patterns show that the compounds are divided in two isomorphous groups: La, Pr, Nd and Eu, Sm, Gd, Tb and Er. For all compounds, the thermodegradation under nitrogen gave the respective oxifluorides (LnOF) as the final product. The melting temperature intervals are 105–110°C, 100–112°C, 90–95°C, 79–101°C, 65–70°C, 75–90°C, 64–76°C and 50–65°C for the La, Pr, Nd, Sm, Eu, Gd, Tb and Er compounds, respectively, and it is verified that the lanthanide contraction induces a weaker intermolecular interaction between adjacent molecules in the solid state.     

Application of an Apple IIe microprocessor for data acquisition and analysis in instrumental neutron activation analysis with a low energy photon detector

The determination of thirteen elements, eleven rare-earth elements (La, Ce, Nd, Sm, Eu, Gd, Tb, Ho, Tm, Tb and Lu), thorium and uranium were performed by instrumental neutron activation analysis for four geological reference materials (G-2, AGV-1, GSP-1 and SY-2) as well as our laboratory rare-earth standard. The analyses were performed using a low energy photon detector coupled to an Apple IIe microprocessor employed as a multichannel analyzer not only to collect the data but also for data analysis. Finally, based on this work we have proposed a simple, rapid routine method for the determination of eleven rare-earth elements, thorium and uranium in geological materials employing IVIC's RV-1 nuclear reactor.     

Rare-earth tricyanomelaminates [NH(4)]Ln[HC(6)N(9)](2)[H(2)O](7)H(2)O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy): structural investigation, solid-state NMR spectroscopy, and photoluminescence

The rare-earth tricyanomelaminates, [NH(4)]Ln[HC(6)N(9)](2)[H(2)O](7)xH(2)O (LnTCM; Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy), have been synthesized through ion-exchange reactions. They have been characterized by powder as well as single-crystal X-ray diffraction analysis, vibrational spectroscopy, and solid-state (1)H, (13)C, and (15)N MAS NMR spectroscopy. The X-ray powder pattern common to all nine rare-earth tricyanomelaminates LnTCM (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) indicates that they are isostructural. The single-crystal X-ray diffraction pattern of LnTCM is indicative of non-merohedral twinning. The crystals are triclinic and separation of the twin domains as well as refinement of the structure were successfully carried out in the space group P1 for LaTCM (LaTCM; P1, Z=2, a=7.1014(14), b=13.194(3), c=13.803(3) A, alpha=90.11(3), beta=77.85(3), gamma=87.23(3) degrees , V=1262.8(4) A(3)). In the crystal structure, each Ln(3+) is surrounded by two nitrogen atoms from two crystallographically independent tricyanomelaminate moieties and seven oxygen atoms from crystal water molecules. The positions of all of the hydrogen atoms of the ammonium ions and water molecules could not be located from difference Fourier syntheses. The presence of [NH(4)](+) ions as well as two NH groups belonging to two crystallographically independent monoprotonated tricyanomelaminate moieties has only been confirmed by subjecting LaTCM to solid-state (1)H, (13)C, and (15)N{(1)H} cross-polarization (CP) MAS NMR and advanced CP experiments such as cross-polarization combined with polarization inversion (CPPI). The (1)H 2D double-quantum single-quantum homonuclear correlation (DQ SQ) spectrum and the (15)N{(1)H} 2D CP heteronuclear-correlation (HETCOR) spectrum have revealed the hydrogen-bonded (N--HN) dimer of monoprotonated tricyanomelaminate moieties as well as H-bonding through [NH(4)](+) ions and H(2)O molecules. The structures of the other eight rare-earth tricyanomelaminates (LnTCM; Ln=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) have been refined from X-ray powder diffraction data by the Rietveld method. Photoluminescence studies of [NH(4)]Eu[HC(6)N(9)](2)[H(2)O](7)xH(2)O have revealed orange-red (lambda(max)=615 nm) emission due to the (5)D(0)-(7)F(2) transition, whereas [NH(4)]Tb[HC(6)N(9)](2)[H(2)O](7)xH(2)O has been found to show green emission with a maximum at 545 nm arising from the (5)D(4)-(7)F(5) transition. DTA/TG studies of [NH(4)]Ln[HC(6)N(9)](2)[H(2)O](7)xH(2)O have indicated several phase transitions associated with dehydration of the compounds above 150 degrees C and decomposition above 200 degrees C.     

Determination of dissociation constants for some pyrogallol azo derivatives and stability constants of their complexes with rare-earth metals

The dissociation constants of some haloazo derivatives of pyrogallol and the stability constants of their complexes with rare-earth metals (La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) are determined by potentiometric titration in aqueous ethanol (3: 7). A correlation between the dissociation constants of the reagents and the stability constants of their complexes is found.     

General synthesis and structural evolution of a layered family of Ln8(OH)20Cl4 x nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y)

The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water molecules per formula weight, n, changed from 6.6 for the high-hydration Gd sample to 6.0 for the low-hydration Gd sample. Also, the hydration number usually decreased with increasing atomic number; e.g., n = 7.4, 6.3, 7.2, and 6.6 for high-hydration Nd, Sm, Eu, and Gd, and n = 6.0, 5.8, 5.6, 5.4, and 4.9 for low-hydration Gd, Tb, Dy, Ho, and Er. The variation in the average Ln-O bond length with decreasing size of the lanthanide ions is also discussed. This family of layered lanthanide compounds highlights a novel chemistry of interplay between crystal structure stability and coordination geometry with water molecules.     

稀土螯合物发光体LB膜的研究(I)

稀土有机配合物的发光研究近年来取得了可喜的近展.铕(Ⅲ)、铽(Ⅲ)、钐(Ⅲ)与β-二酮(β-dik),三正辛基氧化膦(TOPO)所形成的螯合物,以及它们的硝酸盐与邻菲咯啉(Phen)所形成的螯合物都是高光效的发光体,有广阔的应用前景,在某些方面已获得应用.如能把这些具有发光功能的稀土螯合物组装成有序的分子组合体,则很可能在分子光学技术,光电子技术等领域发挥重要作用.如何组装?本文用LB 膜技术,通过交替成膜或混     

Quantum-chemical calculations of the tautomeric forms of azo derivatives of acetylacetone and determination of the stability constants of their complexes with rare-earth metals

The effective atomic charges in the tautomeric forms (enol-azo, keto-azo, and hydrazo) of 3-(2-hydroxy-5-nitro-3-sulfophenylazo)pentane-2,4-dione (L¹), 3-(2-hydroxy-3,5-disulfophenylazo)pentane-2,4-dione (L²), 3-(5-chloro-2-hydroxy-3-sulfophenylazo)pentane-2,4-dione (L³), 3-(2-hydroxy-4-nitrophenylazo)pentane-2,4-dione (L⁴), and 3-(2-hydroxyphenylazo)pentane-2,4-dione (L⁵) were calculated by the Hückel method (MO LCAO). It was found that the hydrazo form is most reactive for meta- and meta’-substituted derivatives (L^1–3) and the keto-azo form is most reactive for para-substituted (L⁴) and unsubstituted ones (L⁵). The stability constants of complexes of rare-earth metals (La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) with L^1–5 determined by potentiometric titration decrease in the order: Lu > Yb > Tm > Er > Ho > Dy > Tb > Gd > Eu > Sm > Nd > Ce > La. Functionalization of the aromatic part of ligands L affected neither the rare-earth metal: L ratio (1: 2) nor the above order of the stability constants.