- A structural variant to the NaErCl4/α-NiWO4 type for ternary rare-earth halides NaMCl4: Synthesis and crystal structure of NaLuCl4
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Single crystals of NaLuCl4 (orthorhombic, Pbcn (Nr. 60), Z = 4, a = 618.6(1) pm, b = 1592.2(2) pm, c = 657.0(1) pm) were grown for the first time from the binary components using the Bridgman technique. The crystal structure may be derived from a hexagonally closest packing of Cl- spheres with one half of all octahedral sites occupied by the cations Na+ and Lu3+, respectively. The close relation of the structure to that of NaErCl4 (α-NiWO4) is discussed. NaScCl4 was found to be isotypic to NaLuCl4. Johann Ambrosius Barth 1996.
- Wickleder, Mathias S.,Güdel, Hans U.,Armbruster, Thomas,Meyer, Gerd
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Read Online
- Syntheses and structural properties of rare earth carbodiimides
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Crystalline samples of rare earth carbodiimides were synthesized by solid-state metathesis reactions of rare earth trichlorides with lithium cyanamide in sealed silica ampules. Two distinct structures were determined by single-crystal X-ray diffraction. The structure determined for Sm 2(CN2)3 [C2/m, Z = 2, a = 14.534(2) A, b = 3.8880(8) A, c = 5.2691(9) A, β = 95.96(2)°, R 1 = 0.0267, and wR2 = 0.0667] was assigned for RE 2(CN2)3 compounds with RE = Y, Pr, Nd, Sm, Gd, Tb, Dy, Ho, and Er, and the structure determined for Lu2(CN 2)3 [R32, Z = 3, a = 6.2732(8) A, c = 14.681 (2) A, R1 = 0.0208, and wR2 = 0.0526] was assigned for the smallest rare earth ions with RE = Tm, Yb, and Lu by powder X-ray diffraction. Both types of crystal structures are characterized by layers of [NCN]2- ions whose arrangements can be derived from the motif of a closest packed layer of sticks. These layers alternate with layers of rare earth ions in a one-by-one sequence. Different tilting arrangements of the N-C-N-axes relative to the stacking directions (c) and different arrangements of RE 3+ ions within metal atom layers account for the two distinct structures in which Sm3+ and Lu3+ ions adopt the coordination numbers 7 and 6, respectively.
- Neukirch, Michael,Tragl, Sonja,Meyer, H.-Jurgen
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Read Online
- Self-assembled light lanthanide oxalate architecture with controlled morphology, characterization, growing mechanism and optical property
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Flower-like Sm2(C2O4)3· 10H2O had been synthesized by a facile complex agent assisted precipitation method. The flower-like Sm2(C2O 4)3·10H2O was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, thermogravimetry- differential thermal analysis and photoluminescence. The possible growth mechanism of the flower-like Sm2(C2O4) 3·10H2O was proposed. To extend this method, other Ln2(C2O4)3·nH2O (Ln = Gd, Dy, Lu, Y) with different morphologies also had been prepared by adjusting different rare earth precursors. Further studies revealed that besides the reaction conditions and the additive amount of complex agents, the morphologies of the as-synthesised lanthanide oxalates were also determined by the rare earth ions. The Sm2(C2O4) 3·10H2O and Sm2O3 samples exhibited different photoluminescence spectra, which was relevant to Sm 3+ energy level structure of 4f electrons. The method may be applied in the synthesis of other lanthanide compounds, and the work could explore the potential optical materials.
- He, Hongmei,Zhang, Youjin,Zhu, Wei,Zheng, Ao
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p. 1546 - 1552
(2011/10/01)
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- Lanthanide carbonates
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The crystal and molecular structures of the rare earth carbonates with the general formulae [C(NH2)]3 [Ln(CO3)4 (H2O)]·2H2O (where Ln = Pr3+,Nd 3+,Sm3+,Eu3+,Gd3+,Tb 3+)and [C(NH2)]3 [Ln(CO3) 4]·2H2O (where Ln = Y3+,Dy 3+,Ho3+,Er3+, Tm3+,Yb 3+,Lu3+) were determined. The crystals consist of monomeric [Ln(CO3)4 (H2O)] 5-or [Ln(CO3)4] 5-complex anions in which the carbonate ligands coordinate to the Ln3+ion in a bidentate manner. The spectroscopic (UV/Vis/NIR and IR) properties of the crystalline lanthanide carbonates, as well as their aqueous solutions, were determined. Correlation between the spectroscopic and the structural data enabled us to conclude that the [Ln(CO3)4 (OH)]6-and [Ln-(CO 3)4]5- species predominate in the light and heavy lanthanide solutions, respectively. The nature of the Ln-O interaction was also discussed. The experimental data, as well as the theoretical calculations, indicated that the Ln-O(CO3 2-) bond is more covalent than the Ln-O(OH2) bond. Moreover, the covalency degree is larger for the heavy lanthanide ions. Inspection of the NBO results revealed that the oxygen hybrids, with the approximate composition sp4, form strongly polarized bonds with the 6s6p5d4 hybrids of lutetium. 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
- Janicki, Rafal,Starynowicz, Przemyslaw,Mondry, Anna
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p. 3601 - 3616
(2011/10/11)
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- Synthesis, characterization and thermal behaviour of solid-state tartrates of heavy trivalent lanthanides and yttrium(III)
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Solid state Ln2-L3 compounds, where Ln stands for heavy trivalent lanthanides (terbium to lutetium) and yttrium, and L is tartrate [(C4H4O6)-2] have been synthesized. Simultaneous thermogra
- Ambrozini, B.,Dametto, P. R.,Ionashiro, M.
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p. 867 - 871
(2011/10/31)
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- Comparison of covalency in the lanthanide chloride and nitrate complexes based on the adsorption data on zeolite y
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The changes of the distribution constants Kd of lanthanide chlorides in the system: zeolite Y (solid phase)-sodium chloride (aqueous phase) were investigated. The evident tetrad effect in the change of log Kd values within the lantha
- G?adysz-P?aska, Agnieszka,Majdan, Marek,Ferenc, Wies?awa,Sarzyński, Jan
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p. 469 - 474
(2012/03/22)
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- Structural characterization of methanol substituted lanthanum halides
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The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(μ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75·5.25(MeOH)]+0.25 [LaBr3.25·4.75(MeOH)]-0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(μ-Cl)]2 (6) and [La(MeOH)9](I)3·MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4-6 were slightly higher in comparison to their hydrated counterparts.
- Boyle, Timothy J.,Ottley, Leigh Anna M.,Alam, Todd M.,Rodriguez, Mark A.,Yang, Pin,Mcintyre, Sarah K.
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p. 1784 - 1795
(2010/07/03)
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- Synthesis, characterization and thermal behaviour of heavy lanthanide and yttrium pyruvates in the solid state
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Solid-state Ln-L compounds, where Ln stands for heavy trivalent lanthanides or yttrium (III) (Tb-Lu, Y) and where L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-R
- Siqueira,De Carvalho,Rodrigues,Ionashiro,Bannach,Ionashiro
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- Synthesis, characterization and thermal behaviour of solid-state 3-methoxybenzoates of heavy trivalent lanthanides and yttrium(III)
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Solid-state Ln(L)3 compounds, where Ln stands for trivalent Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, and L is 3-methoxybenzoate, have been synthesized. X-ray powder diffractometry, infrared spectroscopy, complexometry and elemental analysis were used to characterize the compounds. Inorder to study the thermal behaviour of these compounds simultaneous th ermogravimetry and differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC) were used. The results provided information on the composition, dehydration, polymorphic transformation, thermal stability and thermal decomposition of the synthesized compounds.
- Dametto, P. R.,Ambrozini, B.,Siqueira, A. B.,Carvalho, C. T.,Ionashiro, M.
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p. 933 - 940
(2011/01/06)
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- Preparation, stability and thermodynamic properties of Nd- and Lu-doped BaCeO3 proton-conducting ceramics
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The preparation of BaCeO3 doped by neodymium and lute-tium oxides (BaCe0.8Nd0.2O2.9, BaCe 0.8Lu0.2O2.9) has been performed by solid-state reactions of BaCO3 and CeOsu
- Matskevich, Nata I.,Wolf, Thomas,Matskevich, Mariya Yu.,Chupakhina, Tatiana I.
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p. 1477 - 1482
(2009/07/10)
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- Comparison of thermal properties of lanthanide trimellitates prepared by different methods
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By diffusion in gel medium new complexes of formulae: Nd(btc) ·6H2O, Gd(btc)·4.5H2O and Er(btc)?5H2O (where btc=(C6H3(COO)33-) were obtained. Isomorphous compounds were crystallized in the
- Lyszczek, Renata
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p. 833 - 838
(2009/02/07)
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- 2-Methoxybenzylidenepyruvatewith heavier trivalent lanthanides and yttrium(III): Synthesis and characterization
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Solid-state Ln(2-MeO-BP) compounds, where Ln stands for trivalent Eu to Lu and Y(III) and 2-MeO-BP (which is 2-methoxybenzylidenepyruvate) have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanni
- Ionashiro,Bannach,Siqueira,De Carvalho,Rodrigues,Ionashiro
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p. 953 - 959
(2009/02/01)
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- Synthesis, characterization and thermal behaviour of solid 2-methoxybenzoates of trivalent metals
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Solid-state Ln(L)3 compounds, where Ln stands for trivalent Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and L is 2-methoxybenzoate have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanni
- Siqueira,Carvalho,Ionashiro,Bannach,Rodrigues,Ionashiro
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p. 945 - 951
(2009/02/01)
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- Synthesis, potentiometric, kinetic, and NMR studies of 1,4,7,10- tetraazacyclododecane-1,7-bis(acetic acid)-4,10-bis(methylenephosphonic acid) (DO2A2P) and its complexes with Ca(II), Cu(II), Zn(II) and lanthanide(III) ions
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A cyclen-based ligand containing trans-acetate and trans- methylenephosphonate pendant groups, H6DO2A2P, was synthesized and its protonation constants (12.6, 11.43, 5.95, 6.15, 2.88, and 2.77) were determined by pH-potentiometry and 1H NMR spectroscopy. The first two protonations were shown to occur at the two macrocyclic ring N-CH 2-PO32- nitrogens while the third and fourth protonations occur at the two phosphonate groups. In parallel with protonation of the two -PO32- groups, the protons from the NH +-CH2-PO32- are transferred to the N-CH2-COO- nitrogens. The stability constants of the Ca2+, Cu2+, and Zn2+ (ML, MHL, MH2L, and M2L) complexes were determined by direct pH-potentiometry. Lanthanide(III) ions (Ln3+) form similar species, but the formation of complexes is slow; so, out-of-cell pH-potentiometry (La 3+, Eu3+, Gd3+, Y3+) and competitive spectrophotometry with Cu(II) ion (Lu3+) were used to determine the stability constants. By comparing the log KML values with those of the corresponding DOTA (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4, 7,10-tetraacetic acid) and DOTP (H8DOTP = 1,4,7,10- tetraazacyclododecane-1,4,7,10-tetramethylenephosphonic acid) complexes, the order DOTA 2+ complexes, for which the order is reversed. The relaxivity of Gd(DO2A2P) decreases between pH 2 and 7 but remains constant in the pH range of 7 1 = 3.6 mM-1 s-1). The linewiths of the 17O NMR signals of water in the absence and presence of Gd(DO2A2P) (at pH = 3.45 and 8.5) between 274 and 350 K are practically the same, characteristic of a q = 0 complex. Detailed kinetic studies of the Ce3+ and Gd3+ complexes with DO2A2P showed that complex formation is slow and involves a high stability diprotonated intermediate Ln(H2DO2A2P)*. Rearrangement of the diprotonated intermediate into the final complex is an OH- assisted process but, unlike formation of Ln(DOTA) complexes, rearrangement of Ln(H2DO2A2P)* also takes place spontaneously likely as a result of transfer of one of the protons from a ring nitrogen to a phosphonate group. The order of the OH- assisted formation rates of complexes is DOTA > DO2A2P > DOTP while the order of the proton assisted dissociation rates of the Gd3+ complexes is reversed, DOTP > DO2A2P > DOTA. 1H and 13C NMR spectra of Eu(DO2A2P) and Lu(DO2A2P) were assigned using two-dimensional correlation spectroscopy (2D COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear chemical shift correlation (HETCOR), and exchange spectroscopy (EXSY) NMR methods. Two sets of 1H NMR signals were observed for Eu(DO2A2P) characteristic of the presence of two coordination isomers in solution, a twisted square antiprism (TSAP) and a square antiprism (SAP), in the ratio of 93% and 7%, respectively. Line shape analysis of the 1H NMR spectra of Lu(DO2A2P) gave lower activation parameters compared to La(DOTP) for interconversion between coordination isomers. This indicates that the Ln(DO2A2P) complexes are less rigid probably due to the different size and spatial requirements of the carboxylate and phosphonate groups.
- Kalman, Ferenc K.,Baranyai, Zsolt,Toth, Imre,Banyai, Istvan,Kiraly, Robert,Bruecher, Ernoe,Aime, Silvio,Sun, Xiankai,Sherry, A. Dean,Kovacs, Zoltan
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p. 3851 - 3862
(2009/02/02)
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- Hydrothermal synthesis and luminescent properties of LuBO3: Tb3+ microflowers
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Hexagonal vaterite-type LuBO3:Tb3+ microflower-like phosphors have been successfully prepared by an efficient surfactant- and template-free hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectrometry, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-obtained phosphor samples present flowerlike agglomerates composed of nanoflakes with thickness of 40 nm and high crystallinity in spite of the moderate reaction temperature of 200°C. The reaction mechanism has been considered as a dissolution/precipitation mechanism; the self-assembly evolution process has been proposed on homocentric layer-by-layer growth style. Under ultraviolet excitation into the 4J8→ 4f7d transition of Tb3+ at 248 nm (or 288 nm) and low-voltage electron beam excitation, LuBO3:Tb3+ samples show the characteristic green emission of Tb3+ corresponding to 5D4 → 7F6,5,4,3 transitions with the 5D 4 → 7F5 transition (542 nm) being the most prominent group, which have potential applications in fluorescent lamps and field emission displays.
- Yang, Jun,Zhang, Cuimiao,Wang, Lili,Hou, Zhiyao,Huang, Shanshan,Lian, Hongzhou,Lin, Jun
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p. 2672 - 2680
(2009/02/07)
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- Thermal and spectroscopic investigations of new lanthanide complexes with 1,2,4-benzenetricarboxylic acid
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The new 1,2,4-benzenetricarboxylates of lanthanide(III) of the formula Ln(btc)?nH2O, where btc is 1,2,4-benzenetricarboxylate; Ln is La-Lu, and n=2 for Ce; n=3 for La, Yb, Lu; and n=4 for Pr-Tm were prepared and characterized by elemental analy
- Lyszczek
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p. 533 - 539
(2008/10/09)
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- A systemic study of stepwise chlorination-chemical vapor transport characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by alkaline chlorides as complex former
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A systematic study has been carried out for the stepwise chlorination-chemical vapor transport (SC-CVT) characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by the vapor complexes KLnCl4 and NaLnCl4 (Ln = Sc, Y and La-Lu) used NaCl and KCl as complex former, respectively. The results showed that the SC-CVT characteristics are similarly for NaCl and KCl as complex former, the main deposition temperature of the rare earth chlorides LnCl3 is in the increasing order ScCl3 3 3, and then with a systematically decreasing trend from the early lanthanide chlorides to the end one. The results also showed that the total transported amount of the produced chlorides is YCl3 > ScCl3, and they are much higher than that of most lanthanoid chlorides. For lanthanoids, the total transported amount of chloride increases systematically from the early lanthanoid chlorides to the end one except for EuCl3 and GdCl3 mediated by KCl and NaCl as complex former, respectively, which showed the divergence effect of Gd in the total transport efficiency. But there are some differences in SC-CVT characteristics of pure rare earth oxide mediated by KCl and NaCl as complex former, that is the main deposition temperature region for the same rare earth element was lower for KCl than that for NaCl as complex former except for LaCl3, CeCl3, YbCl3 and LuCl3, while the total transport amount of rare earth chloride for KCl as complex former is higher than that for NaCl except for LaCl3 and EuCl3. More over, the discussion was carried out for Sc and Y on the one hand and the lanthanides contain 4f electron as another hand based on the 4f electron hybridization assumption. Further more, the transport characteristics of rare earth oxides with alkaline chlorides as complex former in this study were compared to that with AlCl3 as complex former.
- Sun, Yan-Hui,He, Peng,Chen, Hua-Ni
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p. 352 - 358
(2008/10/09)
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- Synthesis, characterization and thermal behaviour of solid-state compounds of yttrium and lanthanide benzoates
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Solid-state Ln(Bz)3?H2O compounds where Ln stands for trivalent yttrium or lanthanides and Bz is benzoate have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), X-ray powder diffractometry, infra
- Locatelli,Rodrigues,Siqueira,Ionashiro,Bannach,Ionashiro
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p. 737 - 746
(2008/10/09)
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- Synthesis, characterization and thermal behaviour of solid 4-methoxybenzoates of heavier trivalent lanthanides
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Solid-state Ln-4-MeO-Bz compounds, where Ln stands for trivalent Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and 4-MeO-Bz is 4-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scan
- Rodrigues, Emanuel C.,Siqueira, Adriano B.,Ionashiro, Elias Y.,Bannach, Gilbert,Ionashiro, Massao
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p. 149 - 155
(2008/10/09)
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- Synthesis, characterization and thermal studies on solid compounds of 2-chlorobenzylidenepyruvate of heavier trivalent lanthanides and yttrium(III)
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Solid-state compounds of general formula LnL3· nH 2O, where Ln represents heavier lanthanides and yttrium and L is 2-chlorobenzylidenepyruvate, have been synthesized. Chemical analysis, simultaneous thermogravimetry-differential anal
- Bannach,Schnitzler,Treu Filho,Utuni,Ionashiro
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p. 233 - 240
(2008/10/09)
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- Equilibria and structure of the lanthanide(III)-2-hydroxy-1,3- diaminopropane-N,N,N′,N′-tetraacetate complexes: Formation of alkoxo-bridged dimers in solid state and solution
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The complex formed between 1,3-diamino-2-hydroxypropane-N,N,N′, N′-tetraacetic acid (H4L-OH) and Nd3+ at pH 7.5 was found to be a dinuclear dimer in the solid state by X-ray crystallography. In the complex K4[Nd2(L-O)2-(H2O) 2]-14H2O each ligand is coordinated to both Nd 3+ atoms with an iminodiacetate group (the Nd3+-Nd 3+ distance is 3.9283(8) A). The alcoholic OH groups are deprotonated, and the alkoxo oxygens are coordinated to both Nd3+ in a bridging position. The Nd3+ ions are nine-coordinated with one water molecule per Nd(III) ion in the inner sphere. The complex K 4[Nd2(L-O)2(H2O)2] ·14H2O has an inversion center, and the space group is P1. Two of the K+ counterions are six-coordinated, while the other two K+ ions are eight-coordinated; polar polymeric water-K+ layers are formed between the apolar ligand layers via the bridging water molecules. The dinuclear dimer complexes are also present in aqueous solution. The proton relaxivities of the Gd3+ complex decrease with the increase of pH, and at pH > 6, the low relaxivity values indicate the probable absence of H2O in the inner sphere and the predominance of the eight-coordinated dimer species [Gd2(L-O)2]. 4- The results of ESI-TOF MS studies of the complexes of La 3+, Nd3+, and Lu3+ proved the formation of dinuclear dimers in dilute (0.25 mM) solutions. pH-potentiometric titrations indicate the formation of complexes with 1:1 (Ln(L-OH)-, Ln(HL-OH), and Ln2(L-O)24-) and 2:1 (Ln 2(L-O)+) metal-to-ligand ratios. The stability constants of the Ln(L-OH)- species increase from La3+ (log K = 10.19) to Lu3+ (log K = 14.08). The alcoholic OH group of the Ln(L-OH)- species dissociates at unusually low pH values. The pH range of dissociation shifts to lower and lower pH's with the increasing atomic number of the lanthanides. This pH range is about 4-7 for the La3+ complex and 1-4 for the Lu3+ complex. The results of 1D and 2D 1H and 13C NMR studies of the La3+ complex, the number and multiplicity of signals, and the values of coupling constants are in agreement with the dinuclear dimer structure of the complex in solution.
- Tircso, Gyula,Benyei, Attila,Bruecher, Erno,Kis, Anita,Kiraly, Robert
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p. 4951 - 4962
(2008/10/09)
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- Synthesis, characterization, thermal stability, reactivity, and antimicrobial properties of some novel lanthanide(III) complexes of 2-(N-salicylideneamino)-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene
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Two series of new lanthanide(III) complexes of the type [Ln(HSAT) 2(H2O)3Cl3] and [Ln(HSAT) 2(NO3)3], where Ln = La, Pr, Nd, Sm, Eu, Gd, Dy, Tm, Yb, or Lu, and HSAT = 2-(N-salicy
- Mohanan,Devi
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p. 600 - 609
(2008/10/09)
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- Fullerides: Heterometallic superconductors with composition M2M′C60 (M = K, Rb; M′ = Yb, Lu, Sc)
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One- or two-step reactions of potassium and rubidium fullerides with composition Mk C60 (M = K, Rb; k = 3-6) and K 6C60 + m K mixtures (m = 1, 3) with anhydrous salts M′Cl3 (M′ = La, Pr, Nd, Sm, Gd, Tb, Yb, Lu, Y, Sc) and YbI2 in a toluene-THF medium afforded heterometallic fullerides M3- n M′n C60 (n = 1-3). Among these compounds, substituted fullerides with composition M2M′C60 (M′ = Yb, Lu, Sc) display superconducting properties with critical temperatures of 14-20 K.
- Bulychev,Lunin,Kul'bachinskii,Shpanchenko,Privalov
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p. 1686 - 1692
(2007/10/03)
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- Lanthanide contraction and pH value controlled structural change in a series of rare earth complexes with p-aminobenzoic acid
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A series of rare earth complexes with p-aminobenzoic acid (HL) have been synthesized: [RE2L6(H2O)2] n [RE=La (1), Ce(2), Pr(3), Sm(4), Eu(5), Tb(6), Dy(7), Er(9)] and [RE2L6(H2O)4]·2H 2O [RE=Tb(6′), Ho(8), Yb(10), Lu(11), Y(12)]. The crystal structures of 1, 2, 6, 6′, 7, 9 and 12 have been determined and the isomorphous relationships of the others have been identified. Their structures change from two-dimensional (2D) array (the coordination number of the metal ions is nine for 1 and eight for 2-7 and 9) to double-nuclear structure (the metal ions are eight-coordinated) for 6′, 8 and 10-12, as controlled by lanthanide contraction. The structural type has been found influenced by the pH value of the reaction mixtures.
- Sun, Hao-Ling,Ye, Chao-Hong,Wang, Xin-Yi,Li, Jun-Ran,Gao, Song,Yu, Kai-Bei
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- Organometallic compounds of the lanthanides. 168 [1]: Lanthanidocene complexes containing sulfur-functionalized cyclopentadienyl ligands
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YCl3, SmCl3, and LuCl3 react with 2 equivalents of Na[C5H4CH2CH2SR] (R = Ph (2); Et (3)) yielding (PhSCH2CH2C5H 4)2LnCl (Ln = Y (4a), Sm (4b), Lu (4c)), and (EtSCH 2CH2C5H4)2LuCl (5), respectively. Methylation of 4a, 4c, and 5 with LiMe produces (PhSCH 2CH2C5H4)2LnMe (Ln = Y (6a); Lu (6c)) and (EtSCH2CH2C5H 4)2LuMe (7). YCl3 and LuCl3 react with 1 equivalent of 2 or 3 followed by 1 equivalent Na[C5Me 5] to give (PhSCH2CH2C5H 4)(C5Me5)LnCl (Ln = Y (8a); Lu (8c)) and (EtSCH2CH2C5H4)(C5Me 5)YCl (9). [(EtSCH2CH2C5H 4)(C5Me5)LuCl (10) and 1,10-bipyridine form [(EtSCH2CH2C5H4)-(C 5Me5)Lu(bipy)]+ [(EtSCH2CH 2C5H4)(C5Me5)LuCl 2]- (11). Methylation of 8a, 8c, and 9 with LiMe results in the formation of (PhSCH2CH2C5H 4)(C5Me5)LnMe (Ln = Y (12a); Lu (12c)) and (EtSCH2CH2C5H4)(C5Me 5)YMe (13). LaCl3 and PrCl3 react with 3 equivalents of 3 affording (EtSCH2CH2C5H 4)3Ln (Ln = La (14d) and Pr (14e)), while the reaction of YbI2 with 2 equivalents of 3 gives [(EtSCH2CH 2C5H4)Yb(SCH2CH2C 5H4)]2 (15) along with ethane. The structures of 8c, 11, 14d, and 15 were determined by single-crystal X-ray diffraction.
- Schumann, Herbert,Herrmann, Katja,Muehle, Stefan H.,Dechert, Sebastian
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p. 1184 - 1194
(2008/10/08)
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- Synthesis, characterisation and thermal behaviour of solid stat compounds of 4-methylbenzylidenepyruvate with heavier trivalent lanthanides and yttrium(III)
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Solid state Ln-4-Me-BP compounds, where Ln stands for heavier trivalent lanthanides (gadolinium to lutetium) and yttrium(III) and 4-Me-BP is 4-methylbenzylidenepyruvate (CH3-C6H4-CH=CH-COCOO-), have been synthesized. Eleme
- Marques,Melios,Ionashiro
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p. 145 - 150
(2008/10/08)
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- Interaction of thulium, ytterbium(III) and lutetium chlorides with sodium chloride
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The pseudobinary systems NaCl-LnCl3 (Ln = Tm, Yb, Lu) were investigated by DTA and X-ray diffraction. Two types of ternary chlorides exist: congruently melting compounds Na3LnCl6 with the cryolite-structure, incongruently melting compounds NaLnCl4 with the NaErCl4-Ln (Ln = Tm) or the NaLnCl4-structure (Ln = Yb, Lu). All these structure types contain [LnCl6]-octahedra. By solution calorimetry and e.m.f. measurements in galvanic cells for solid electrolytes could be proved that all compounds are formed from NaCl and LnCl3 by gain in lattice enthalpy.
- Buechel,Seifert
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p. 203 - 208
(2008/10/09)
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- Comparative study for stepwise chlorination-chemical vapor transport characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by the vapor complexes LnAlnCl3n+3
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A systematic study has been carried out for the stepwise chlorination-chemical vapor transport (SC-CVT) characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by the vapor complexes LnAlnCl3n+3 (where Ln = rare earth elements) under identical conditions. The results show that the total transported amount of the produced chlorides is the highest for YCl3; it is also high for ScCl3, but low for LaCl3, and then increases systematically from the early lanthanide chlorides to the end lanthanide chlorides except CeCl3, EuCl3 and GdCl3. The results also show that the main deposition temperature of the chlorides is in the increasing order ScCl3 3 3 and then with a systematically decreasing trend from the early lanthanide chlorides to the end lanthanide chlorides. Based on the literature data for the solid complexes LnAl3Cl12 and LnAl3Br12, a similar coordination structure assumption is introduced for the vapor complexes LnAl3Cl3n+3 from Ln = Sc to Ln = Lu with the same stoichiometry to explain the SC-CVT characteristics of the pure rare earth oxides from Sc2O3 to Lu2O3 using a 4f electron hybridization assumption.
- Wang, Zhi-Chang,Sun, Yan-Hui,Guo, Lei
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p. 109 - 113
(2008/10/08)
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- Macrocyclic tetraazacyclododecane conjugates and their use as diagnostic and therapeutic agents
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A group conjugates having a functionalized polyaminocarboxylate chelant that form complexes with rare earth-type metal ions, covalently attached to an antibody or antibody fragment, can be used for therapeutic and/or diagnostic purposes.
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- Solution enthalpies of hydrates LnCl3·xH2O (Ln=Ce-Lu)
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Trichlorides of the lanthanide elements Ln=Ce-Lu form: (a) isotypic hexahydrates LnCl3·6H2O with a coordination number (CN) 8 for the Ln3+ ions. (b) Two isotypic groups of trihydrates LnCl3·3H2O, in the first group Ln=Ce-Dy the CN is 8; the structure of the second group Ln=Er-Lu is unknown. With Ho no trihydrate exists; a dihydrate is formed. (c) Two isotypic groups of monohydrates LnCl3·H2O with unknown structure - Ln=Ce-Dy and Ln=Ho-Lu. For all compounds and for anhydrous chlorides LnCl3 solution enthalpies were measured with an isoperibolic calorimeter. The ΔsolH0 values do not depend only on the difference (lattice enthalpies/hydration enthalpies), but also on the state in solution. According to Spedding the CN of the Ln3+ ions against water changes from 9 to 8 between Nd and Sm, causing minima in the series of solution enthalpies. Dihydrates LnCl3·2H2O are found for Ln=Ce, Pr, Nd, Sm and presumably for Eu and Gd. They are not yet well characterised.
- Seifert,Funke
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- Thermal decomposition of rare earth complexes with 2-amino-3,5-dichlorobenzoic acid
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The conditions of the thermal decomposition of the 2-amino-3,5-dichloro-benzoates of Y and lanthanides have been studied. During heating in air, the dihydrated complexes Ln(C6H2Cl2NH2COO) 3·2H2/
- Mrozek,Sikorska,Rzaczynska
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p. 707 - 720
(2008/10/09)
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- Thermodynamic Properties of the Rare Earth Element Vapor Complexes LnAl3Cl12 from Ln = La to Ln = Lu
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Systematic analysis of rare earth element complexes has been carefully carried out in the liquid and solid states but not in the gaseous state because of the lack of a complete set of experimental data for any kind of vapor complexes of all rare earth elements. Here we present experimental quenching results which suggest that the LnAl3Cl12 complexes are the predominant vapor complexes roughly in the temperature range 588-851 K and pressure range 0.01-0.22 MPa for all of the 14 rare earth elements Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. For these elements, thermodynamic functions of the reactions LnCl3(s) + 3/2Al2Cl6(g) = LnAl3Cl12(g) were calculated from the measurements. Those for the radioelement Pm were smoothly interpolated. The results show Gd divergences from the standard enthalpies and standard entropies from LaAl3Cl12 to LuAl3Cl12.
- Wang, Zhi-Chang,Wang, Lin-Shan
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p. 1536 - 1540
(2008/10/09)
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- Lanthanide Ion Chelates of Dibenzyl 1,1'-Diacetylferrocenebis(hydrazonatocarbodithioate)
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A new ligand, dibenzyl 1,1'-diacetylferrocenebis(hydrazonatocarbodithioate), Fe[C5H4C(CH3)=NNHCSSCH2C6H5)2] (H2Dafhb) and its chelates with lanthanide ions, Ln(Dafhb)Cl (Ln = lanthanide) have been prepared by the reaction of the H2Dafhb with LnCl3. All compounds were characterized by elemental analyses, IR, (1H) NMR, UV, electrolytic conductivity and TGA measurements. It is shown that the ligand coordinates to the metal in the thiol form and that one chloride ion participates in coordination. The chelates are non-electrolytes in DMF and are more thermostable than the ligand due to formation of chelate rings.
- Gang, Zhao,Yuan, Cao
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p. 1207 - 1217
(2008/10/09)
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- Enthalpy of formation of the lutetium ion in aqueous solution at infinite dilution
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The enthalpies of the reaction of metallic lutetium with 2.19 N HCl and the enthalpies of dissolution of lutetium chloride in aqueous 2.19 N HCl have been measured in a sealed rocking calorimeter at 298.15 K.The enthalpies of formation of the lutetium ion and of lutetium trichloride have been calculated from the results.
- Tiflova, L. A.,Monaenkova, A. S.,Goryushkin, V. F.
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p. 1043 - 1045
(2007/10/02)
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- Neutral monocyclopentadienyllutetium alky is: In search of steric unsaturation
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Addition of a THF solution of NaC5Me5 (1 equiv) to a refluxing THF solution of LuCl3(THF)3 affords after workup [Na(THF·OEt2)]Lu(η5-C5Me 5)Cl3 (1) in ca. 70% yield. Compound 1 reacts cleanly with LiCH(SiMe3)2 in diethyl ether, in the presence of THF (5 equiv) to afford the monoalkyl complex [Li(THF)2]Lu(η5-C5Me 5){CH(SiMe3)2}Cl2 (2) in 69% yield. Addition of tetramethylethylenediamine (TMEDA) to the supernatant liquor after isolation of 2 affords an additional 16% of [Li(TMEDA)]Lu(η5-C5Me5){CH(SiMe 3)2}Cl2 (3). A LiCl-free, mixed alkyl complex, 8, was prepared from reaction of 3 with LiCH2SiMe3 giving initially a mixture of [Li(THF)3]Lu(η5-C5Me5)(CH 2SiMe3){CH(SiMe3)2}Cl (7) and Lu(η5-C5Me5)(CH2SiMe 3){CH(SiMe3)2}(THF) (8). Recrystallization (once) from hexane gave neutral, LiCl-free 8. This is the first reported neutral mixed alkyl organolanthanide complex. The single-crystal X-ray structure determinations of 3 and 7 are reported. In each case the lutetium atom shows a three-legged piano-stool coordination geometry, with the lithium atom in a tetrahedral coordination and linked to the lutetium by one (in 7) or two (in 3) bridging chloride ligands. The lutetium-alkyl bond lengths are 2.367 (6) A? in 3 and 2.394 (16) and 2.344 (18) A? for Lu-CH(SiMe3)2 and 2.353 (17) and 2.314 (18) A? for Lu-CH2SiMe3 for the two distinct molecules of 7, present in the crystal.
- Van Der Heijden, Harry,Pasman, Peter,De Boer, Eric J. M.,Schaverien, Colin J.,Orpen, A. Guy
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p. 1459 - 1467
(2008/10/08)
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- Thermodynamic properties of some lanthanide chlorides
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The heat capacities of the lanthanide chlorides NdCl2, SmCl2, EuCl2, DyCl2, TmCl2, YbCl2, DyCl3, YbCl3 and LuCl3 were measured at 10-320 K with an adiabatic microcalorimeter. Standard thermodynamic properties were calculated from the experimental results. The heat capacities of these chlorides are composed of the lattice heat capacity and an additional contribution caused by the thermal population of the low-lying Stark electronic levels (Schottky anomaly). The Schottky heat capacity was estimated as the difference between the experimental Cp values for the isostructural paramagnetic and diamagnetic chlorides. Experimental Schottky contributions were found to be in good agreement with those calculated for SmCl2, TmCl2 and YbCl3 via a general model of the main-term Stark splitting of the respective ions in the orthorhombic and monoclinic crystal fields.
- Tolmach,Gorbunov,Gavrichev,Iorish
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p. 845 - 849
(2008/10/08)
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- Low-temperature Specified Heat of Dysprosium and Lutetium Trichlorides
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The specific heat of DyCl3 and LuCl3 has been studied by adiabatic calorimetry in the range 6 - 240 K.The values of the thermodynamic functions under standard conditions have been determined.
- Tolmach, P. I.,Gorbunov, V. E.,Gavrichev, K. S.,Totrova, G. A.,Goryushkin, V. F.
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p. 1529 - 1532
(2007/10/02)
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