化学气相传输法分离二元混合重稀土氧化物

稀土气态配合物;化学气相传输法分离二元混合重稀土氧化物     

Synthesis, structure, and thermally stable luminescence of Eu(2+)-doped Ba2Ln(BO3)2Cl (Ln = Y, Gd and Lu) host compounds

A new family of chloroborate compounds, which was investigated from the viewpoint of rare earth ion activated phosphor materials, have been synthesized by a conventional high temperature solid-state reaction. The crystal structure and thermally stable luminescence of chloroborate phosphors Ba(2)Ln(BO(3))(2)Cl:Eu(2+) (Ln = Y, Gd, and Lu) have been reported in this paper. X-ray diffraction studies verify the successful isomorphic substitution for Ln(3+) sites in Ba(2)Ln(BO(3))(2)Cl by other smaller trivalent rare earth ions, such as Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. The detailed structure information for Ba(2)Ln(BO(3))(2)Cl (Ln = Y, Gd, and Lu) by Rietveld analysis reveals that they all crystallize in a monoclinic P2(1)/m space group. These compounds display interesting and tunable photoluminescence (PL) properties after Eu(2+)-doping. Ba(2)Ln(BO(3))(2)Cl:Eu(2+) phosphors exhibit bluish-green/greenish-yellow light with peak wavelengths at 526, 548, and 511 nm under 365 UV light excitation for Ba(2)Y(BO(3))(2)Cl:Eu(2+), Ba(2)Gd(BO(3))(2)Cl:Eu(2+), and Ba(2)Lu(BO(3))(2)Cl:Eu(2+), respectively. Furthermore, they possess a high thermal quenching temperature. With the increase of temperature, the emission bands show blue shifts with broadening bandwidths and slightly decreasing emission intensities. It is expected that this series of chloroborate phosphors can be used in white-light UV-LEDs as a good wavelength-conversion phosphor.     

Reactions of lanthanoid metals with 3,5-diphenylpyrazole at elevated temperatures: synthesis and structures of both homoleptic, [Ln3(Ph2pz)9] (Ln = La, Nd), [Ln2(Ph2pz)6] (Ln = Er, Lu), and heteroleptic, [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er or Yb), pyrazolate complexes

The direct reaction of lanthanoid metals with 3,5-diphenylpyrazole (Ph2pzH) at 300 degrees C under vacuum in the presence of mercury gives the structurally characterized [Ln3(Ph2pz)9] (Ln = La or Nd), [Ln2(Ph2pz)6] (Ln = Er or Lu). Similar reactions provided heteroleptic [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er and Y). The last was obtained only from impure Ph2pzH, but was subsequently prepared by treatment of [Yb(Ph2pz)3(thf)2] with Ph2pzH. Reactions of Yb with Ph2pzH at 200 degrees C gave a poorly soluble divalent species which was converted by 1,2-dimethoxyethane into [Yb(Ph2pz)2(dme)2]. Single crystal X-ray structures established a bowed trinuclear pyrazolate-bridged structure for [Ln3(Ph2pz)9] (Ln = La or Nd), Ln...Ln...Ln being 135.94(1) degrees (La) and 137.41(1) degrees(Nd). There are two eta2-Ph2pz ligands on the terminal Ln atoms and one on the central metal with adjacent Ln atoms linked by one mu-eta2:eta2 and one mu-eta5 (to terminal Ln):eta2 pyrazolate group. Thus the terminal Ln atoms are formally nine-coordinate and the central Ln, ten-coordinate. By contrast, [Ln2(Ph2pz)6] (Ln = Er or Lu) complexes are dimeric with two terminal (eta2) and two bridging (mu-eta2:eta2) pyrazolates and eight-coordinate lanthanoids. All six heteroleptic complexes [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er or Yb) are isomorphous with three equatorial eta2-Ph2pz groups, transoid(N-Ln-N 158.18(6)-161.43(9) degrees) eta1-pyrazole ligands, and eight-coordinate Ln throughout.     

希土硼氢化合物的研究 Ⅷ.二氢二(1-吡咯基)硼酸希土(Ⅲ)的1,10-二氮杂菲配合物

在CHOH-H_2O介质中,通过Ln(phen)_2Cl(Ln=La、Sm、Gd、Dy、Tm、Yb;Phen=1,10—二氮杂菲)与Me_4NBH_2(NC_4H_4)_2反应,制得了化学式为Ln(Phen)_4(BH_2(NC_4H_4)_2)的希土配合物。IR光谱,(11)~BNMR谱和摩尔电导率的结果表明,在配合物中,B原子通过B-H-Ln键与Ln发生单齿配位作用。     

Theoretical study of mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes

The structure, bonding and vibrational properties of the mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes were studied using various quantum chemical methods (HF, MP2 and the Becke3-Lee-Yang-Parr exchange-correlation density functional) in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. Our comparative study indicated the superiority of MP2 theory while the HF and B3-LYP methods as well as less sophisticated basis sets failed for the correct energetic relations. In particular, f polarization functions on Li and X proved to be important for the Li...X interaction in the complexes. From the three characteristic structures of such complexes, possessing 1-(C3v), 2-(C2v), or 3-fold coordination (C3v) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are located considerably lower on the potential energy surface then the monodentate isomer. Therefore only the bi- and tridentate isomers have chemical relevance. The monodentate isomer is only a high-lying local minimum in the case of X = F. For X = Cl, Br, and I this structure is found to be a second-order saddle point. The bidentate structure was found to be the global minimum for the systems with X = F, Cl, and Br. However, the relative stability with respect to the tridentate structure is very small (1-5 kJ/mol) for the heavier halide derivatives and the relative order is reversed in the case of the iodides. The energy difference between the three structures and the dissociation energy decrease in the row F to I. The ionic bonding in the complexes was characterized by natural charges and a topological analysis of the electron density distribution according to Bader's theorem. Variation of the geometrical and bonding characteristics between the lanthanum and dysprosium complexes reflects the effect of "lanthanide contraction". The calculated vibrational data indicate that infrared spectroscopy may be an effective tool for experimental investigation and characterization of LiLnX4 molecules.     

双水杨醛1,10-癸二胺Schiff碱稀土配合物的合成和表征

合成了双水杨醛缩1,10-癸二胺Sch iff碱配体(C24H32N2O2,以L表示)与稀土Ln3+的15种新的固体配合物[LnL(NO3)3].nH2O(Ln=La,Ce,Pr,Nd,Sm,Eu,n=0;Ln=Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y,n=1).利用元素分析、摩尔电导、红外光谱、热分析等方法进行表征.中心金属离子Ln3+与Sch iff碱配体中的酚羟基氧以及硝酸根中的氧发生配位,配位数为8.     

Rare earth metal complexes bearing thiophene-amido ligand: synthesis and structural characterization

2,6-diisopropyl-N-(2-thienylmethyl)aniline (H2L) has been prepared, which reacted with equimolar rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2, afforded rare earth metal mono(alkyl) complexes, LLn(CH2SiMe3)(THF)3 (:Ln=Lu; :Ln=Y). In this process, H2L was deprotonated by one metal alkyl species followed by intramolecular C-H activation of the thiophene ring to generate dianionic species L2- with the release of two tetramethylsilane. The resulting L2- combined with three THF molecules and an alkyl unit coordinates to Y3+ and Lu3+ ions, respectively, in a rare N,C-bidentate mode, to generate distorted octahedron geometry ligand core. Whereas, with treatment of H2L with equimolar Sc(CH2SiMe3)3(THF)2, a heteroleptic complex (HL)(L)Sc(THF) () was isolated as the main product, where the dianionic L2- species bonds to Sc3+ via chelating N,C atoms whilst the monoanionic HL connects to Sc3+ in an S,N-bidentate mode. All complexes have been characterized by NMR spectroscopy and X-ray diffraction analysis.     

Synthesis and structures of the C5Me4SiMe3-supported polyhydride complexes over the full size range of the rare earth series

The acid-base reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] with Cp'H gave the corresponding half-sandwich rare earth dialkyl complexes [(Cp')Ln(CH(2)SiMe(3))(2)(thf)] (1-Ln: Ln=Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp'=C(5)Me(4)SiMe(3)) in 62-90% isolated yields. X-ray crystallographic studies revealed that all of these complexes adopt a similar overall structure, in spite of large difference in metal-ion size. In most cases, the hydrogenolysis of the dialkyl complexes in toluene gave the tetranuclear octahydride complexes [{(Cp')Ln(μ-H)(2)}(4)(thf)(x)] (2-Ln: Ln=Sc, x=0; Y, x=1; Er, x=1; Tm, x=1; Gd, x=1; Dy, x=1; Ho, x=1) as the only isolable product. However, in the case of Lu, a trinuclear pentahydride [(Cp')(2)Lu(3)(μ-H)(5)(μ-CH(2)SiMe(2)C(5)Me(4))(thf)(2)] (3), in which the C-H activation of a methyl group of the Me(3)Si unit on a Cp' ligand took place, was obtained as a major product (66% yield), in addition to the tetranuclear octahydride [{(Cp')Lu(μ-H)(2)}(4)(thf)] (2-Lu, 34%). The use of hexane instead of toluene as a solvent for the hydrogenolysis of 1-Lu led to formation of 2-Lu as a major product (85%), while a similar reaction in THF yielded 3 predominantly (90%). The tetranuclear octahydride complexes of early (larger) lanthanide metals [{Cp'Ln(μ-H)(2)}(4)(thf)(2)] (2, Ln=La, Ce, Pr, Nd, Sm) were obtained in 38-57% isolated yields by hydrogenolysis of the bis(aminobenzyl) species [Cp'Ln(CH(2)C(6)H(4)NMe(2)-o)(2)], which were generated in-situ by reaction of [Ln(CH(2)C(6)H(4)NMe(2)-o)(3)] with one equivalent of Cp'H. X-ray crystallographic studies showed that the fine structures of these hydride clusters are dependent on the size of the metal ions.     

水合希土硝酸盐与本并及单环己基-12-冠-4配合物的合成、性质及晶体结构

在乙腈介质中合成了苯并－１２－冠－４（简称Ｂ－１２－Ｃ－４）和单环己基－１２－冠－４（简称Ｃｙ－１２－Ｃ－４）的六种希土配合物：ＲＥ（ＮＯ３）３·Ｂ－１２－Ｃ－４（ＲＥ＝Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ），ＲＥ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４（ＲＥ＝Ｌａ，Ｌｕ）。研究了它们的ＩＲ及＾１ＨＮＭＲ性质，并测定了四种单晶的结构，用ＩＮＤＯ法计算了Ｌｕ（ＮＯ３）３·Ｂ－１２－Ｃ－４，Ｌｕ（ＮＯ３）３·Ｃｙ－１２－Ｃ     

配合物[Ln(C6H5COO)2(NO3)(Bipy)]2的合成及表征

镧系含杂环胺三元配合物的研究从六十年代至今已进行了大量探索 ,但四元配合物的研究一直不多 ,并且由于联吡啶 (Ｂｉｐｙ)的配位能力相对较弱 ,有关其四元配合物的研究报道更为少见[1～ 3] 。我们探索合成了 [Ｌｎ(Ｃ6 Ｈ5ＣＯＯ) 2 (ＮＯ3)(Ｂｉｐｙ) ]2 ,且在合成过程中首次观察到了热力学与动力学竞争的现象。1　实验部分1 1　试剂和仪器稀土氧化物纯度超过 99.99% (上海跃龙有色金属有限公司 ) ,其余试剂均为分析纯。ＣａｒｌｏＥｒｂａ 1 1 0 6型元素分析仪 ;ＤＤＳ 1 1Ａ型电导率仪 (1 .0× 1 0 -3ｍｏｌ·Ｌ-1ＤＭＦ) ;日本岛津 47…     

间羟基苯甲酸邻菲啰啉稀土三元配合物的合成、表征和抗菌活性研究

本文用间羟基苯甲酸、邻菲口罗啉与碳酸稀土合成了四种新的固体三元配合物,通过元素分析、摩尔电导、红外光谱、Ｘ射线粉末衍射、差热－热重分析等手段,确定配合物的组成为：Ｌｎ（ｐｈｅｎ）Ｌ３,（Ｌｎ＝Ｌａ,Ｇｄ,Ｄｙ,Ｙ;Ｌ＝ｍ－ＨＯ－Ｃ６Ｈ４ＣＯＯ－）,并对配合物的某些性质进行了研究。     

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本文对稀土卤素气态配合物LnMnX3n＋3（M=Al、Fe;X=Cl、Br）和ALnX4（A=碱金属;X=Cl、I）的热力学性质、研究方法及其在稀土分离制备方面的应用进行了综述,并对其今后的研究及应用进行了展望.     

Isoprene polymerization with indolide‐imine supported rare‐earth metal alkyl and amidinate complexes

Reaction of 7‐{(N‐2,6‐R)iminomethyl)}indole ( HL¹ , R = dimethylphenyl; HL² , R = diisopropylphenyl) and rare‐earth metal tris(alkyl)s, Ln(CH₂SiMe₃)₃(THF)₂, generated new rare‐earth metal bis(alkyl) complexes LLn(CH₂SiMe₃)₂(THF) [L = L¹: Ln = Lu ( 1a ), Sc ( 1b ); L = L²: Ln = Lu ( 3a ), Sc ( 3b )] and mono(alkyl) complexes L²₂Lu(CH₂SiMe₃) ( 4a ). Treatment of alkyl complexes 1a and 4a with N,N′‐diisopropylcarbodiimide afforded the corresponding amidinates L¹Lu{iPr₂NC(CH₂SiMe₃)NiPr₂}₂ ( 2a ) and L²₂Lu{iPr₂NC(CH₂SiMe₃)NiPr₂} ( 5a ), respectively. These new rare‐earth metal alkyls and amidinates except 4a in combination with aluminum alkyls and borate generated efficient homogeneous catalysts for the polymerization of isoprene, providing high cis‐1,4 selectivity and high molar mass polyisoprene with narrow molar mass distribution (M_n = 2.65 × 10⁵, M_w/M_n = 1.07, cis‐1,4 98.2%, −60 °C). The environmental hindrance around central metals arising from the bulkiness of the ligands, the Lewis‐acidity of rare‐earth metal ions, the types of aluminum tris(alkyl)s and borate, and polymerization temperature influenced significantly on both the catalytic activity and the regioselectivity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5251–5262, 2008     

Eu2+离子在BaF2-xREF3体系中的f→f跃迁发射

研究了Eu²⁺离子在BaF_2-xREF₃体系中的荧光光谱结构,当RE=La,Gd,Y,Lu和Sc时,降低温度或适当改变基质中阳离子间摩尔比都观察到了EU²⁺的f→f跃迁尖峰发射。     

Reversible coordinative chain transfer polymerization of styrene by rare earth borohydrides,chlorides/dialkylmagnesium systems

The ability of various rare earth borohydride and chloride complexes/n‐butylethylmagnesium systems to operate styrene chain transfer polymerization in mild conditions has been assessed. Thirteen precatalysts have been considered: the rare earth trisborohydrides Ln(BH₄)₃(THF)_x (x = 3, Ln = Nd (1), La (2), Sm (3), x = 2, Ln = Y (4), Sc (5)), the rare earth chlorides LnCl₃(THF)_x (x = 3, Ln = Nd (6), La (7), Sm (8), Y (9), x = 2, Ln = Sc (10)), the mixed La(BH₄)₂Cl(THF)_2.6 (11) and the half‐lanthanidocenes Cp*Ln(BH₄)₂(THF)₂ (Ln = Nd (12), La (13)). Six systems were found to be active precatalysts for the polymerization of styrene. 1 , 2 , and 11 led to an efficient transmetalation of the growing polystyrene chain with the simultaneous occurrence of βH elimination, whereas 7 , 12 , and 13 led to catalyzed chain growth behavior. It is noteworthy that the catalyzed chain growth obtained with 12 and 13 occurs with significant stereoselectivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 802–814, 2010     

Weitere Oxochlorotitanate LnTiO3Cl der Seltenen Erden (LnSm?Lu) - Präparation,Kristallstruktur, elektronenmikroskopische Untersuchung

New Rare Earth Oxochlorotitanates LnTiO₃Cl (Ln?Sm? Lu) - Preparation, Structure and Electron Microscopic Investigations After the preparation of SmTiO₃Cl we made the attempt to prepare analogous compounds with the heavier rare earth elements. We present 2 methods to prepare powders of LnTiO₃Cl (Ln = Sm? Lu) together with a new method to prepare the rare earth oxychlorides LnOCl (Ln = Tm? Lu). There will be also presented 2 methods to get single crystals of these compounds via chemical vapour transport. The new rare earth oxochlorotitanates LnTiO₃Cl (Ln = Eu? Lu) are isotypic to SmTiO₃Cl. They crystallize in the monoclinic space group: C2/m (No. 12). The lattice parameters (Å) are between a = 9.716(3), b = 3.942(2), c = 10.100(4) (SmTiO₃Cl) and a = 9.748(1), b = 3.8454(5), c = 9.625(2) (LuTiO₃Cl), Z = 4. We observed a permanent decay of the cell volume with the decay of the radii of the cations. The structure of EuTiO₃Cl and DyTiO₃Cl was refined to R = 3.4% and R = 5.8% respectively. The crystal structure which has a certain similarity to brannerite can be described in a simplified way by saying that the rare earth and chlorine particles are located between walls of Ti? O-double-octahedra.     

希土硼氢化物的研究--Ⅴ.十二氢十二硼酸N-氧化邻二氮杂菲合希土(Ⅲ)螯合物的合成

将希土氧化物或氢氧化物同N-氧化邻二氮杂菲及十二氢十二硼酸在水—乙醇介质中反应,合成了十三个十二氢十二硼酸N-氧化邻二氮杂菲合希土螯合物。通过元素分析、红外光谱、摩尔电导率的测量。确定螯合物的化学式为[Ln(phenO)_4]_2(B_(12)H_(12))_3·nH_2O。用DTA—TG法探讨了化合物的热行为。     

A convenient route to lanthanide triiodide THF solvates. Crystal structures of LnI(3)(THF)(4) [Ln = Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y

The reaction between 1.5 equiv of elemental iodine and rare earth metals in powder form in THF at room temperature gives the rare earth triiodides LnI(3)(THF)(n)() in good yields. Purification by Soxhlet extraction of the crude solids with THF reliably gives the THF adducts LnI(3)(THF)(4) [Ln = La, Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Sm, Gd, Dy, Er, Tm, Y] as microcrystalline solids. X-ray crystallography reveals that the early, larger lanthanide iodide PrI(3)(THF)(4) crystallizes as discrete molecules having a pentagonal bipyramidal structure, whereas the later, smaller lanthanide iodides LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y] crystallize as solvent-separated ion pairs [LnI(2)(THF)(5)][LnI(4)(THF)(2)] in which the cations adopt a pentagonal bipyramidal geometry and the anions adopt an octahedral geometry in the solid state.     

Syntheses, structures and properties of seven isomorphous 1D Ln3+complexes Ln(BTA)(HCOO)(H2O)3 (H2BTA = bis(tetrazoly)amine, Ln = Pr, Gd, Eu, Tb, Dy, Er, Yb) and two 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr, Nd)

Seven isomorphous 1D chain Ln3+ complexes Ln(BTA)(HCOO)(H2O)3 (Ln = Pr (1), Gd (2), Eu (3), Tb (4) Dy (5), Er (6) and Yb (7)), and two formate coordinating and bridging 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr (8) and Nd (9)) have been synthesized and characterized by single crystal X-ray diffraction analysis. Although the Ln3+ ions in 1-7 have different radius, the trivalent lanthanide ions in 1-7 show the same coordinated environment. The well-defined single crystal structures of 8 and 9 are first samples for formate-bridged Ln3+ metallic complexes. The luminescent properties of solid samples of 2-5 at room temperature and the magnetic property of 2 have been also reported and discussed in this paper.     

Isostructural neo-pentoxide derivatives of group 3 and the lanthanide series metals for the production of Ln2O3 nanoparticles

The synthesis and characterization of a series of neo-pentoxide (OCH2C(CH3)3 or ONep) derivatives of group 3 and the lanthanide (Ln) series' metals were undertaken via an amide/alcohol exchange route. Surprisingly, the products isolated and characterized by single-crystal X-ray diffraction yielded isostructural species for every trivalent cation studied: [Ln(mu-ONep)2(ONep)]4 [Ln=Sc (1), Y (2), La (3), Ce (4), Pr (5), Nd (6), Sm (7), Eu (8), Gd (9), Tb (10), Dy (11), Ho (12), Er (13), Tm (14), Yb (15), Lu (16)]. Compounds 3, 4, 6, and 11 have been previously reported. Within this series of complexes, the Ln metal centers are oriented in a square with each Ln-Ln edge interconnected via two mu-ONep ligands; each metal center also binds one terminal ONep ligand. NMR data of 1-3 indicate that the solid-state structure is retained in solution. FTIR spectroscopy (KBr pellet) revealed the presence of significant Ln---H-C interactions within one set of the bridging ONep ligands in all cases; the stretching frequencies of these C-H bonds appear to increase in magnitude with decrease in metal ion radius. These complexes were used to generate nanoparticles through solution hydrolysis routes, resulting in the formation of lanthanide oxide nanoparticles and rods. The emission properties of these ceramics were preliminarily investigated using UV-vis and PL measurements.