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. …     

Spektroskopische und strukturelle Charakterisierung von Tris(2, 6‐di‐t‐butyl‐phenolato)lanthanid(III) (Ln(OAr′)3; Ln = Pr,Nd) sowie parametrische Analyse des Kristallfeld‐Aufspaltungsmusters von Nd(OAr′)3

Electronic Structures of Highly Symmetrical Compounds of f Elements. 37 [1] Spectroscopic and Structural Characterization of Tris(2, 6‐di‐t‐butyl‐phenolato)lanthanide(III) (Ln(OAr′)₃; Ln = Pr, Nd), and Parametric Analysis of the Crystal Field Splitting Pattern of Nd(OAr′)₃ Pr(OAr′)₃ and Nd(OAr′)₃ crystallize (at approximately 150 K and 200 K, respectively) in the monoclinic space group P2₁ with four molecules in the unit cell. If one considers only the directly coordinating oxygen atoms, the effective crystal field is of C_3v symmetry. The signals in the optical spectra of Pr(OAr′)₃ are broad using either solutions or solids, even at ca. 80‐90 K, thus they are not suitable for interpretation purposes. Nd(OAr′)_3, however, exhibits sharp absorption bands at room and low temperatures, which are assigned in analogy to the previously identified absorption transitions of Nd[N(SiMe₃)₂]₃ based on optical polarization measurements. The thus derived crystal field splitting pattern is simulated by fitting the free parameters of a phenomenological Hamiltonian, achieving a reduced r.m.s. deviation of 26.4 cm^—1 for 64 assignments. The parameters used allow the estimation of the ligand field strength associated with the (OAr′)^— ligand, the insertion of this ligand into empirical nephelauxetic and relativistic nephelauxetic series, and the setup of experimentally‐based non‐relativistic and relativistic molecular orbital schemes in the f range.     

生理条件下稀土及钙,锌离子与L—羟脯氨酸配位作用的研究

生理条件下稀土及钙、锌离子与Ｌ－羟脯氨酸配位作用的研究＊高峰＊＊牛春吉孟淑兰倪嘉缵（中国科学院长春应用化学研究所稀土化学和物理开放实验室长春１３００２２）金天柱王瑞瑶王祥云（北京大学稀土材料化学和应用国家重点实验室北京１００８７１）关键词稀土钙锌Ｌ－...     

Yb2+3—xPd12—3+xP7 (x = 0.40): Different Ytterbium Species in a Substituted Structural Motif of the Zr2Fe12P7 Type

The new compound Yb_2+3—xPd_12—3+xP₇ x = 0.40(4)) was synthesized by sintering of a mixture of elemental components at 1100 °C with subsequent annealing at 800 °C. The crystal structure of Yb_2+3—xPd_12—3+xP₇ was solved and refined from X‐ray single‐crystal diffraction data: space group P6¯, a = 10.0094(4)Å, c = 3.9543(2)Å, Z = 1; R(F) = 0.022 for 814 observed unique reflections and 38 refined parameters. The atomic arrangement reproduces a structure motif of the hexagonal Zr₂Fe₁₂P₇ type in which one of the transition metal positions is substituted predominantly by ytterbium (Yb : Pd = 0.86(1) : 0.14). The ytterbium atoms are embedded in the 3D polyanion formed by palladium and phosphorus atoms. Two different environments for ytterbium atoms are present in the structure. Magnetic susceptibility measurements and XAS spectroscopy at the Yb L_III edge show the presence of ytterbium in two electronic configurations, 4?¹³ and 4?¹⁴. The following model was derived. Ytterbium atoms in the 3k site are in the 4?¹³ state, the two remaining positions contain ytterbium in intermediate‐valence states, giving totally 79 % ytterbium in the 4?¹³ electronic configuration.     

Crystal Structures and Thermal Behaviour of Lanthanide(III) Hexanoate 1, 10‐Phenanthroline Complexes, [M(C5H11CO2)3(phen)] and [Tm(C5H11CO2)2(NO3)(phen)]

Lanthanide(III) hexanoate 1, 10‐phenanthroline complexes crystallise in the space group P2₁/n. The compounds consist of dimers, whereby two lanthanide ions are held together by two bidentate bridging and two tridentate bridging carboxylate groups. The first coordination sphere of the lanthanide ions is completed by one bidentate chelating carboxylate group and by one bidentate 1, 10‐phenanthroline molecule, resulting in the coordination number 9. The dimers have a spherical form, which has important consequences for the thermal properties of complexes. The basic idea behind the preparation of this type of compounds is the stabilisation of the ionic lanthanide layer, so that the smaller lanthanide ions (from which the normal alkanoates do not show mesomorphism because they are too small) show liquid crystallinity. The stabilisation of the ionic layer was successful, expressed by the high melting temperatures, but mesomorphism is not observed. The absence of mesomorphism is related to the isotropic structure of the compounds. A lower symmetry is obtained when a hexanoate group is replaced by a nitrate group. Thulium(III) dihexanoate nitrate 1, 10‐phenanthroline crystallises in the space group P1¯. However, this compound also shows a spherical dimeric structure, but no mesomorphism.     

YGa3—xCrxB4O12的合成,发光与磁性

扩展了ＹＧａ３Ｂ４Ｏ１２的合成温度。研究了合成的改变及Ｃｒ＾３＋离子引入后发光性质的变化。合成ＹＧａ３－ｘＣｒｘＢ４Ｏ１２化合物后，对其磁学性质进行了表征。结果表明，高温合成该化合物有利于人合物芝光发射的增强，掺杂少量Ｃｒ＾３＋可以稳定该化合物春发光光谱。磁化率随Ｃｒ＾３＋含量的增加而增大。     

铂—稀土合金的高温氧化与挥发

研究了铂和铂－稀土合金在７００－１４００℃相对静止空气中的氧化与挥发，其动力学曲线不仅符合Ｆｉｃｋ定律，而且与Ｊ－ＭＡ方程吻合较好，在１１００℃以上Ｐｔ的挥发很大，添加 土元素后大大改善了Ｐｔ的抗氧化能力，Ｐｔ的挥发主要取决于表面扩散，而Ｐｔ－ＲＥ合金的氧化受控于晶界扩散。     

Solvent extraction of lanthanide ions with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP), II. Extraction of erbium(III), ytterbium(III) and lutetium(III) by HPMBP from aqueous-methanol solutions

The solvent extraction of lanthanides(III) (Ln=Er, Yb, Lu) by 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HL) in carbon tetrachloride from aqueous-methanol phase was investigated. The equilibrium constants for the extraction from aqueous –50% (v/v) methanol phase (K _ex ), two-phase stability constants of the complexesLnL ₃ ( ₃ ^* ) and stability constants of complexesLnL ²⁺,LnL ₂ ⁺ ,LnL ₃ ( _n ) (Ln=Yb, Lu) were calculated. It was confirmed that the addition of methanol to the aqueous phase causes a synergistic effect. The influence of methanol on the dissociation constant of HPMBP (K _a ) and the distribution constant of HPMBP (p _HL ) between carbon tetrachloride and water-methanol solutions was investigated.

---

Extraktion von Seltenerdmetall-Ionen mit 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HPMBP), II. Extraktion von Er(III), Yb(III) und Lu(III) aus Wasser-Methanol-Lösungen

Zusammenfassung Die Extraktion von Lanthaniden (Ln=Er, Yb, Lu) mittels 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HL) in Kohlenstofftetrachlorid aus Wasser-Methanol Phase wurde untersucht. Die Werte der Gleichgewichtskonstante für Extraktion aus Wasser –50% (v/v) Methanol-Phase (K _ex ), der zweiphasigen Beständigkeitskonstante für die KomplexeLnL ₃ ( ₃ ^* ), sowie der Stabilitätskonstante des KomplexesLnL ²⁺,LnL ₂ ⁺ undLnL ₃ ( _n ) (Ln=Yb, Lu), wurden berechnet. Es wurde festgestellt, daß die Zugabe von Methanol zur wäßrigen Phase einen synergistischen Effekt hat. Der Einfluß von Methanol auf die Dissoziationskonstante von HPMBP (K _a ) und die Verteilungskonstante des HPMBP (p _HL zwischen organischer und wäßrig-methanolischer Phase wurde untersucht.

     

掺铽聚丙烯薄膜的研究

合成了化学组成为Ｙ１－ｘＴｂｘＬ３和Ｌａ１－ｘＴｂｘＬ３（Ｌ＝Ｃ８Ｈ７Ｏ２）的两种荧光粉，将其掺杂到聚丙烯中，制得两种聚丙烯荧光薄膜，通过测试机械性能，微分扫描式量热法分析，紫外分光光谱和荧光光谱测定，研究膜的物理和荧光性能。结果表明：这两种掺铽聚丙烯膜在３６５或２５４ｎｍ紫外光激发下，都能发出黄绿色荧光。掺入Ｙ１－ｘＴｂｘＬ３的聚丙烯膜的荧光强度大于掺Ｌａ１－ｘＴｂｘＬ３的聚丙烯膜。     

Synthesis and Determination of Standard Molar Enthalpies of Formation for Complexes of Rare Earth Isothiocyanates with Glycine

Four solid complexes of rare earth isothiocyanates with glycine were synthesized. They were characterized by chemical analysis, elemental analysis, Infrared spectra, X-ray powder diffraction and TO-DSC analysis. Their chemical formulae were proved to be RE(NCS)2.Gly .H2O, where RE is La, Ce, Pr or Nd. The integral heats of solution of RE(NCS)3.3Gly. H2O in water, of RE(NCS)2. 7H2O in aqueous glycine solution and of glycine in water have been measured calorimetricaliy at 298. 15K. By means of a thermochemical cycle suggested in this paper, the standard molar enthalpies of formation for RE(NCS)2. 3Gly.H2O(c) were obtained and their lattice energies were calculated.