The first ruthenium-alkyne-dihydride reported is now recognized as an intermediate in the homogeneous hydrogenation of diphenylacetylene: Crystal structure of (μ-H)2Ru3(CO)9(μ3-η2-∥-C2Ph2)

The title complex (complex1) was the first alkyne-substituted triruthenium dihydrido cluster to be reported and was characterized by spectroscopy as a triangular cluster with the alkyne parallel to a Ru-Ru edge. Recently, we have found that1 is a key intermediate in the homogeneous hydrogenation of diphenylacetylene catalyzed by tetrahedral Ru₄ and FeRu₃ clusters. Since the discovery of1, a great number of complexes with alkynes parallel to a cluster edge have been reported; at present this is the more common bonding mode for alkynes on trinuclear clusters. The structural features of1 allow a comparison with those of other ruthenium-containing derivatives and help to draw suggestions of the role of1 in hydrogenation catalysis.     

Er~(3 ),Ho~(3 )和Tm~(3 )在硫氧化钆中的余辉发光

非放射性长余辉磷光粉作为美化和清洁光源在发光陶瓷、交通安全标志、紧急突发事件的照明设施、工艺美术涂料等众多领域得到越来越广泛的应用,引起人们的重视.到目前为止,文献报道的稀土长余辉磷光体的激活离子主要有铕离子(Eu3+和Eu2+[1-4]、三价铈离子(Ce3+)[5]、三价铽离子(Tb3+)[6]、三价镨离子(Pr3+)[7]、三价钐离子(Sm3+)[8].Ho3+,Er3+,Tm3+等稀土离子作为红外上转换发光材料的激活离子[9～12],而关于它们的长余辉发光的报道极少.最近,雷炳富等在Tm3+离子[13]激活的硫氧化钇体系中发现了长余辉发光.在此,我们通过高温固相法合成了Er3+,Ho3+和Tm3+掺杂的硫氧化钆长余辉磷光粉,观察到该体系中迄今未见文献报道的Er3+,Ho3+和Tm3+离子的长余辉发光.     

Structural and Optical Properties of Sol-Gel Derived Aluminosilicate Planar Waveguides Doped with Er3+ Ions

Er3+ doped-aluminosilicate thin films were prepared on silica and silica/Si substrates by the sol-gel process and dip-coating. The sol-gel aluminosilicate planar waveguides were prepared from silicon and aluminium alkoxides. Their structural characterization has been carried out by Raman spectroscopy, Atomic Force and Scanning Electron Microscopies. The results indicated that these films present an amorphous structure until an annealing temperature of 900°C, while at temperatures higher than 1000°C, crystallization occurs. An estimate of microcrystallite sizes using Raman spectroscopy is given, which agrees with data from scanning electron microscopy. The optical properties have been investigated by Fluorescence spectroscopy in the visible region.     

Syntheses and Crystal Structure of Erbium(Ⅲ) Coordination Polymers with Two Flexible Double Betaine Ligands

1INTR0DUCTI0NLanthanidecarboxylatecomplexeshavebeenwidelystudiedt1iandm0starefoundtoexhibitavarietyofdimericorinfinitechainstructures.Recentstudiesinourlaboratoryhavedem0nstratedthattheprototypetertiaryaminebetaine(Me,N CHzC0z-)anditsderivativesareusefulinthegenerationoflanthanidecarb0xylate-likecomplexeswithnewstructuralfeaturesduetotheiroverallchargeneutralityandpossibleinclusionofvariouskindsofcounteranionsinthestructuret2~4i.Thelan-thanidecomplexesisolatedsofarhavebeenfoundtobemononu…     

长链氨羧络合剂萃取稀土饵

研究了长链氨羧络合剂N,N′-二(十二烷基)乙二胺二乙酸钠(Na2R2Y)的氯仿溶液萃取稀土饵的行为;考察了溶液酸度、络合剂浓度、相比和温度对萃取率的影响.用摩尔比法测定了Na2R2Y与Er3+的络合摩尔比为1∶1;结果表明,Na2R2Y的氯仿溶液对饵的萃取率随络合剂浓度的增大而增大,随温度的升高而降低.     

Complex lanthanide chromate(VI)-phosphates K2R(CrO4)(PO4) (R = Dy-Lu, Y)

The conditions of formation of complex lanthanide chromate(VI)-phosphates K₂R(CrO₄)(PO₄) were found and these compounds were synthesized by solid-state synthesis with variation of the starting compounds, the temperature of synthesis (500–800 °C), and the annealing time (6–200 h). These salts are typical of late lanthanides, R = Dy-Lu, Y. Using lutetium derivatives as examples, it was shown that no similar compounds with lithium or sodium are formed. All the complex chromate(VI)-phosphates obtained decompose under static conditions at temperatures above 550 °C. They are isostructural and crystallize in the monoclinic system. The unit cell parameters for thulium, ytterbium, and lutetium compounds were calculated. It is shown by IR spectroscopy that PO₄ tetrahedra in the crystal lattice of potassium lanthanide chromate(VI)-phosphates are substantially distorted, whereas the CrO₄ tetrahedra retain the regular tetrahedron symmetry (T _d ). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 622–626, April, 2006.     

三硒化二铒Er_2Se_3的合成与结构

采用高温固相反应和化学气相传输法合成三硒化二铒。晶体属于四方晶系，Ｍ_ｒ＝５７１．４０，空间群为Ｐ４／ｎｍｍ，ａ＝３．９８４（１），ｃ＝８．２２８（３），Ｖ＝１３０．５９（７），Ｚ＝１，Ｄ_ｃ＝７，２７ｇ／ｃｍ￣３，Ｆ（０００）＝２３８，μ（ＭｏＫα）＝５２８．８６ｃｍ￣（－１），对于１８７个Ｉ≥３σ（Ｉ）的独立衍射点，最后偏离因子Ｒ＝０．０６６，Ｒ_ｗ＝０．０７８。化合物Ｅｒ_２Ｓｅ_３的晶体结构是由Ｅｒ配位多面体的双层状结构通过共用Ｓｅ（２）原子，沿ｃ轴方向堆积而形成的三维结构。     

STUDIES ON cis-trans-ISOMERIZATION AND REACTION KINETICS OF A μ, η~2-VINYL LIGAND IN A TRIOSMIUM CLUSTER

The dihydride cluster H_2O_(s_3)(CO)_(10) reacts with ethyne to give a cis-adduct [O_(s_3)H(μ,η~2-CH=CH_2)(CO)_(10)]. The high deuterated cluster D_2O_(s_3)(CO)_(10), the reaction of D_2O_(s_3)(CO)_(10)with ethyne C_2H_2 to form the vinyl product cluster [O_(s_3)D(μ, η~2-CH=CHD)(CO)_(10)], and thereaction of H_2O_(s_3)(CO)_(10) with the deuterated ethyne C_2D_2 to form [O_(s_3)H(μ,η~2-CD=CDH)(CO)_(10)] have been reported primarily in this paper. The two cis-adducts undergo cis-trans-isomerization of μ,η~2-vinyl ligands under a small amount of the nucleophile pyridine. Usingthe combination of deuteration and dynamic ~1H,~2H NMR spectra, we report the experimen-tal evidence determined by the dynamic ~1H, ~2H NMR spectra, mechanism, and kinetic dataof the isomerization.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

Er3+，Ho3+和Tm3+在硫氧化钆中的余辉发光

The new Er^3 , Ho^3 and Tm^3 doped gadolinium oxysulfide phosphors with the long afterglow emission were synthesized by solid-state reaction method. The synthesized phosphors were characterized by X-ray diffraction. The excitation and photolumineseenee spectra, afterglow spectra and afterglow decay curve were examined by fluorescence spectroscopy. The afterglow spectra of Gd2O2S:Er^3 , Mg, Ti showed typical transitions of Er^3 at 528(2H11/2→4I15/2), 548 (^4S3/2 →^4I15/2) and 669 nm (^4F9/2→^4I15/2). In the afterglow spectra of Gd2O2S: Ho^3 , Mg, Ti,typical transitions of Ho^3 at 546 nm (^5S2→^5I8), 651 and 661 nm (^2F5→^5I8) were observed. In Gd2O2S:Tm^3 , Mg,Ti, the afterglow emission at 800 nm (^1G4→^3H5) of Tm^3 was seen. The meehnism and model of afterglow energy transfer were proposed.