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1.
Reactions of La(III), Pr(III), Nd(III) or Sm(III) nitrate with bifunctional tetradentateSchiff base, [o-HOC6H4C(CH3): :NCH2]2, having the donor system HO–N–N–OH in 12 molar ratio have been investigated and found to yield new derivatives of the type [Ln(SBH2)2](NO3)3 [whereLn=La(III), Pr(III), Nd(III) or Sm(III) andSBH2=Schiff base molecule, [o-HOC6H4C(CH3) : NCH2]2. On the basis of elemental analyses, conductivity and magnetic measurements and infrared spectra, plausible structures for the resulting complexes have been indicated.  相似文献   

2.
The rare-earth metal(III) oxide selenides of the formula La4O4Se[Se2], Ce4O4Se[Se2], Pr4O4Se[Se2], Nd4O4Se[Se2], and Sm4O4Se[Se2] were synthesized from a mixture of the elements with selenium dioxide as the oxygen source at 750 degrees C. Single crystal X-ray diffraction was used to determine their crystal structures. The isostructural compounds M4O4Se[Se2] (M=La, Ce, Pr, Nd, Sm) crystallize in the orthorhombic space group Amm2 with cell dimensions a=857.94(7), b=409.44(4), c=1316.49(8) pm for M=La; a=851.37(6), b=404.82(3), c=1296.83(9) pm for M=Ce; a=849.92(6), b=402.78(3), c=1292.57(9) pm for M=Pr; a=845.68(4), b=398.83(2), c=1282.45(7) pm for M=Nd; and a=840.08(5), b=394.04(3), c=1263.83(6) pm for M=Sm (Z=2). In their crystal structures, Se2- anions as well as [Se-Se]2- dumbbells interconnect {[M4O4]4+} infinity 2 layers. These layers are composed of three crystallographically different, distorted [OM4]10+ tetrahedra, which are linked via four common edges. The compounds exhibit strong Raman active modes at around 215 cm(-1), which can be assigned to the Se-Se stretching vibration. Optical band gaps for La4O4Se[Se2], Ce4O4Se[Se2], Pr4O4Se[Se2], Nd4O4Se[Se2], and Sm4O4Se[Se2] were derived from diffuse reflectance spectra. The energy values at which absorption takes place are typical for semiconducting materials. For the compounds M4O4Se[Se2] (M=La, Pr, Nd, Sm) the fundamental band gaps, caused by transitions from the valence band to the conduction band (VB-CB), lie around 1.9 eV, while for M=Ce an absorption edge occurs at around 1.7 eV, which can be assigned to f-d transitions of Ce3+. Magnetic susceptibility measurements of Ce4O4Se[Se2] and Nd4O4Se[Se2] show Curie-Weiss behavior above 150 K with derived experimental magnetic moments of 2.5 micro B/Ce and 3.7 micro B/Nd and Weiss constants of theta p=-64.9 K and theta p=-27.8 K for the cerium and neodymium compounds, respectively. Down to 1.8 K no long-range magnetic ordering could be detected. Thus, the large negative values for theta p indicate the presence of strong magnetic frustration within the compounds, which is due to the geometric arrangement of the magnetic sublattice in form of [OM4]10+ tetrahedra.  相似文献   

3.
Two series of complexes of meconic acid (H3 Mec) with rare-earths have been prepared by varying the preparative procedure. The compounds have the general formulae, [Ln(Mec) (H2O)2]·3 H2O (whereLn=La, Ce, Pr, Nd, Sm, Ho and Y) and [Ln(HMec) (H2 Mec) (H2O)2]·4 H2O (whereLn=La, Pr, Nd and Sm). The infrared spectral data indicate that the carboxylate groups are bound to the rare-earth metal in a bidentate fashion. Thermal studies indicate that two water molecules are coordinated in each case. The complexes are probably polymeric.
Komplexe von Seltenerd-Metallen mit Meconsäure
Zusammenfassung Es wurden zwei Reihen von Komplexen der Meconsäure (H3 Mec) mit Seltenerd-Metallen mit den allgemeinen Formeln [Ln(Mec)(H2O)2]·3 H2O (Ln=La, Ce, Pr, Nd, Sm, Ho, Y) und [Ln(HMec)2(H2 Mec) (H2O)2]·4 H2O (Ln=La, Pr, Nd, Sm) hergestellt. Die IR-Spektren zeigen, daß die Carboxylat-Gruppen in zweizähniger Weise mit den Metallionen koordinieren; thermische Untersuchungen ergeben, daß in beiden Reihen jeweils zwei Wassermoleküle zusätzlich koordiniert sind. Die Komplexe weisen wahrscheinlich eine Polymerstruktur auf.
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4.
Summary p-Aminosalicylates of Y, La and lanthanides prepared in the reaction of the ammoniump-aminosalicylate and lanthanide chlorides in solutions have the general formulaLn(C7H6O3N)3·nH2O, wheren=3 for La, Ce;n=2 for Pr, Nd, Sm, Eu;n=0 for Y, Gd—Lu. Their solubilities in water are of the order of 10–3 mol dm–3. Heating above 350–450 K leads to dehydration and decomposition at the same time. The IR and X-ray spectra for the obtained complexes were recorded. It was found that only complexes of La—Nd are crystalline compounds. The way of metal-ligand coordination is discussed.
Darstellung und Charakterisierung der Komplexe von Seltenen Erdmetallen mitp-Aminosalicylsäure
Zusammenfassung Zur Darstellung der Verbindungen des TypsLn(C7H6O3N)3·nH2O (mitn=3 für La, Ce;n=2 für Pr, Nd, Sm, Eu;n=0 für Y, Gd—Lu) wurde die berechnete Menge von Ammonium-p-aminosalicylat undLnCl3-Lösungen beipH5.8 gemischt und zur Kristallisation gebracht. Ihre Wasserlöslichkeit bei 298 K ist in der Größenordnung 10–3 mol dm–3. Beim Erhitzen erfolgt bei 350–450 K Entwässerung und Zersetzung zugleich. Die Infrarot- und Röntgenspektren der erhaltenen Komplexe wurden gemessen und dabei festgestellt, daß nur die La—Nd-Komplexe kristalline Verbindungen sind. Die Art der Koordination der Seltenerdmetalle mit den Liganden wird diskutiert.
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5.
Industrial sediments of calcium sulfate semihydrate obtained from industrial extraction phosphoric acid and containing 0.3–4.5 wt % of impurity La?Sm are investigated by energy-dispersive X-ray fluorescence analysis (XRFA) and a procedure for the quantitative determination of cerium lanthanides in the sediments is developed. The use of linear regression analysis of X-ray fluorescence spectra of multielement industrial samples and models of individual compounds NaLn(SO4)2 · H2O (cp grade) allowed us to resolve overlaps of spectral L-series lines for La–Sm, eliminate the background, and perform the regression assessment of line intensities of these elements. On this basis, we developed a procedure for the determination of La, Ce, Pr, Nd, and Sm in CaSO4 · 0.5H2O sediments with limits of detection (wt %): 0.022, 0.013, 0.011, 0.008, and 0.008, respectively. In concentration ranges (wt %) La (0.05–0.99), Ce (0.1–4.9), Pr (0.005–0.49), Nd (0.02–0.99), and Sm (0.005-0.19), the relative standard deviation RSD (n = 10, P = 0.95) was 18?27, 9?18, 20?31, 17?26, and 19?31%, respectively. A comparison of the results of XRFA with the data of inductively coupled plasma mass spectrometry confirms the accuracy of the results obtained according to OST (Branch Standard) 41-08-221-04.  相似文献   

6.
The layered manganese oxides LnBaMn1.96Fe0.04Oy (Ln=Y, Gd, Sm, Nd, Pr, La) have been synthesized for y=5,5.5 and 6. In the oxygen-saturated state (y=6) they exhibit the charge and orbital order at ambient temperature for Ln=Y, Gd, Sm, but unordered eg-electronic system for Ln=La, Pr, Nd. Fourfold increase of quadrupole splitting was observed owing to the charge and orbital ordering. This is in agreement with the jumplike increase in distortion of the reduced perovskite-like cell for the charge and orbitally ordered manganites compared to the unordered ones. Substitution of 2% of Mn by Fe suppresses the temperatures of structural and magnetic transitions by 20–50 K. Parameters of the crystal lattices and the room-temperature Mössbauer spectra were studied on 40 samples whose structures were refined within five symmetry groups: P4/mmm, P4/nmm, Pm-3m, Icma and P2/m. Overwhelming majority of the Fe species are undifferentiated in the Mössbauer spectra for most of the samples. Such the single-component spectra in the two-site structures are explained by the preference of Fe towards the site of Mn(III) and by the segmentation of the charge and orbitally ordered domains.  相似文献   

7.
Preparation and Crystal Structure of (4-Picolinium)[LnCl4(H2O)3] (Ln = La, Ce, Pr, Nd) The complex water containing chlorides (4-Picolinium)[LnCl4(H2O)3] (Ln = La, Ce, Pr, Nd) were prepared for the first time, and the crystal structures of (4-Picolinium)[LnCl4(H2O)3] (Ln = La, Pr) were determined on single crystals by X-ray methods. The isotypic compounds crystallize with triclinic symmetry, space group P1 , Z = 2. Surprisingly there exist the dimeric complex anions [Ln2Cl8(H2O)6]2? (Ln = La, Pr).  相似文献   

8.
Synthesis and Crystal Structures of Lanthanide Bromide Thiosilicates Ln3Br[SiS4]2 (Ln = La, Ce, Pr, Nd, Sm, Gd) Single crystals of the bromide—thiosilicates Ln3Br[SiS4]2 were prepared by reaction of lanthanide metal (Ln = La, Ce, Pr, Nd, Sm, Gd), sulfur, silicon and bromine in quartz glass tubes. The thiosilicates crystallize in the monoclinic spacegroup C2/c (Z = 4) isotypically to the iodide analogues Ln3I(SiS4)2 and the A—type chloride—oxosilicates Ln3Cl[SiO4]2 with the following lattice constants: La3Br[SiS4]2: a = 1583.3(4) pm, b = 783.0(1) pm, c = 1098.2(3) pm, β = 97.33(3)° Ce3Br[SiS4]2: a = 1570.4(3) pm, b = 776.5(2) pm, c = 1092.2(2) pm, β = 97.28(2)° Pr3Br[SiS4]2: a = 1562.6(3) pm, b = 770.1(2) pm, c = 1088.9(2) pm, β = 97.50(2)° Nd3Br[SiS4]2: a = 1561.4(4) pm, b = 766.0(1) pm, c = 1085.3(2) pm, β = 97.66(3)° Sm3Br[SiS4]2: a = 1555.4(3) pm, b = 758.5(2) pm, c = 1079.9(2) pm, β = 98.28(2)° Gd3Br[SiS4]2: a = 1556.5(3) pm, b = 750.8(1) pm, c = 1074.5(2) pm, β = 99.26(2)° In the crystal structures the bromide ions form chains along [001] with trigonal planar coordination by lanthanide cations, while the [SiS4]4‐—building units display isolated distorted tetrahedra.  相似文献   

9.
The compounds LnSrScO4, where Ln=La, Ce, Pr, Nd and Sm, have been synthesized. Rietveld profile analysis of powder X-ray diffraction data collected at room temperature reveal that the compounds possess a modified K2NiF4-type structure with orthorhombic cell symmetry formed by tilting of the ScO6 octahedra. Variable temperature (25-1200 °C) powder X-ray diffraction data show that at the highest temperatures the structures of LaSrScO4 and PrSrScO4 transform to the regular tetragonal K2NiF4-structure type but the degree of orthorhombicity (c/a) in the unit cells initially increases on heating for all materials, reaching a maximum near 300 °C. This structural behavior is analyzed in terms of relative ionic radii of the various lanthanides and scandium. A general structural model based on tolerance factors has been developed for the family of materials A2BO4 with various A and B cation sizes.  相似文献   

10.
《Analytical letters》2012,45(10):1885-1895
Abstract

High purity lanthanum oxide was analysed to determine traces of Ce, Pr, Nd, and Sm by employing inductively coupled plasma atomic emission spectrometry (ICP-AES). Lanthanum oxide was dissolved in nitric acid and the solution was nebulized into the plasma generated by a RF generator (56 MHz; 1.5kW). Analytical lines of Ce, Pr, Nd, and Sm, which were free of interference from the spectral lines of both La and the other rare earths, were scanned on a Jobin-Yvon, Model JY-38 THR-1000 1m-Czerny-Turner monochromator. Standards containing the four analytes (Ce, Pr, Nd, and Sm) in the concentration range 0.01–0.2 μg/ml and La at 2 mg/ml were used for calibration. Detection limits ranged between 6 and 16 ng/ml for the four analytes in aqueous solution.  相似文献   

11.
The ternary rare-earth zinc antimonides REZn1-xSb2 (RE=La, Ce, Pr, Nd, Sm, Gd, Tb) were prepared by heating at 1050 °C followed by annealing at 600 °C. For all members, single-crystal X-ray diffraction studies indicated that the Zn deficiency is essentially fixed, corresponding to the formula REZn0.6Sb2, with no appreciable homogeneity range. These compounds adopt the HfCuSi2-type structure (Pearson symbol tP8, space group P4/nmm, Z=2). Single-crystal electrical resistivity measurements confirmed the occurrence of an abrupt resistivity decrease near 4 K for RE=Ce, and a less pronounced one for RE=La, Pr, and Gd. Except for the ferromagnetic Ce (Tc=2.5 K) and antiferromagnetic Tb (TN=10 K) members, all remaining compounds exhibit no long-range magnetic ordering down to 2 K, instead showing temperature-independent (RE=La), van Vleck (RE=Sm), or Curie-Weiss paramagnetism (RE=Pr, Nd, Gd).  相似文献   

12.
A series of lanthanide penta-germanides LnGe5 (Ln=Ce, Pr, Nd and Sm) has been prepared by high-pressure (5–13 GPa) and high-temperature (500–1200 °C) reaction. CeGe5 crystallizes in an orthorhombic unit cell (S.G. Immm (71)) with a=4.000(5) Å, b=6.192(5) Å, c=9.86(1) Å, and V=244.1(5) Å3. The new germanides are isotypic with LaGe5 consisting of a Ge covalent network with tunnels where guest ions Ln3+ are situated. The network is composed of sublayers with edge-sharing Ge six-membered rings with only boat conformation. The sublayers are connected by rare eight-coordinated Ge atoms. The cell volume of the compounds systematically decreases from La to Sm compounds, except for CeGe5, owing to the lanthanide contraction. The lattice constants of CeGe5 are smaller than those of the Pr compound because it contains Ce4+ ions. CeGe5 is paramagnetic above 2 K, but does not obey the Curie–Weiss law. PrGe5 and NdGe5 are Curie–Weiss type paramagnets with Weiss temperatures of –3.3 and –18.4 K. SmGe5 shows an antiferromagnetic transition at 10.4 K.  相似文献   

13.
Two new series of ternary gallides with the chemical formulas (La, Ce, Pr, Nd, Sm)AuxGa4−x and (La, Ce, Pr, Nd, Sm)Au1.5Ga2.5 were synthesized from the elements by arc melting. From X-ray powder diffraction analysis the REAuxGa4−x series of compounds was found to be isotypic and crystallize with BaAl4 type of structure; the homogeneity range at 600°C of each of the REAuxGa4−x phases was established, revealing remarkable deviations from Vegard's rule. At 600°C the REAuxGa4−x phases of the BaAl4 type were observed to be in thermodynamic equilibrium with a structure variant crystallizing at the composition REAu1.5Ga2.5 and with a narrow homogeneous range. In case of PrAu1.5Ga2.5 the structure type was refined from X-ray single-crystal counter data (CaBe2Ge2 type, space group P4/nmm, Rw = 0.046). Gold and gallium atoms were generally found on separate crystallographic sites; however, a statistical distribution of 51% Au + 49% Ga was derived for the 2b sites. 197Au Mössbauer spectroscopy confirmed the occupational mode of the gold atoms in CeAu1.5Ga2.5. For the BaAl4-type phases, X-ray powder and Mössbauer data revealed preferential occupation of the 4e sites of I4/mmm by gold atoms; practically no Au was observed on the 4d sites. Magnetic susceptibilities were determined over a temperature range extending from 2 to 1100 K. Above liquid nitrogen temperatures the paramagnetic behavior of the (Ce, Pr, Nd)AuxGa4−x and the (Ce, Pr, Nd)Au1.5Ga2.5 compounds is characterized by magnetic moments close to the ideal trivalent rare earth values. Lanthanum compounds are diamagnetic, whereas SmAuxGa4−x alloys are characterized by a typical Van Vleck-type paramagnetism of closely spaced multiplets. At very low temperatures onset of ferromagnetic ordering is observed for the BaAl4-type series of compounds. No superconductivity was encountered down to 2 K.  相似文献   

14.
The rare earth borides RERu4B4 (RE = Ce, Pr, Nd, Sm) were synthesized from the elements by arc‐melting and their crystal structures were studied on the basis of X‐ray powder and single‐crystal diffraction: LuRu4B4 type, I41/acd, a = 747.47(8), c = 1506.4(3) pm, wR2 = 0.0579, 362 F2 values for CeRu4B4, a = 751.3(2), c = 1507.1(5) pm, wR2 = 0.0724, 471 F2 values for PrRu4B4, a = 751.0(2), c = 1506.9(6) pm, wR2 = 0.0598, 384 F2 values for NdRu4B4, and a = 749.1(1), c = 1506.0(3) pm, wR2 = 0.0759, 413 F2 values for SmRu4B4, with 18 variables per refinement. Striking structural motifs of the RERu4B4 structures are Ru4 tetrahedra and B2 dumbbells with Ru–Ru and B–B distances of 271 and 180 pm in CeRu4B4. The intermediate valence of cerium leads to shorter Ce–Ru distances of 292 pm. CeRu4B4 behaves like a Pauli paramagnet with a small room temperature susceptibility of 1.5 × 10–4 emu · mol–1. Chemical bonding analyses shows substantial Ru–B and B–B bonding within the [Ru4B4] substructure.  相似文献   

15.
Preparation and Crystal Structure of LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) and Thermal Decomposition to LnBr3 LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) was prepared in crystalline form for the first time. The crystal structures of LaAl3Br12, PrAl3Br12, and NdAl3Br12 were determined on single crystals by X-ray methods. The isotypic compounds crystallize with trigonal symmetry, space group P 3112, Z = 3. A structural comparison to lanthanoide chloroaluminates of equal composition is given and thermal decomposition of LnAl3Br12 (Ln = Nd) to the corresponding lanthanoide tribromide is described.  相似文献   

16.
The lanthanide complexes of bis(benzimidazole-2′-yl-methyl)amine (BImz) having molecular formula [M(BImz)X3H2O]·nH2O (M = La, Pr, Nd, or Gd; X = Cl or ClO4 and n = 1, 2 or 3) were prepared and characterized spectroscopically through IR, 1H and 13C NMR, FAB-mass, UV–visible and luminescence spectroscopy. TGA data suggested presence of coordinated and the lattice water. The oscillator strengths of the f–f transitions and the covalency parameters (β, b1/2 and δ) have been evaluated from the electronic spectral data. The proposed hepta-coordinate geometry for the complexes has been ascertained from the molecular model computations. CV studies indicate formation of a stable quasi-reversible redox couple GdIII/IV in the solution. The in vivo antimicrobial activities of the complexes have been evaluated against gram +ve and gram −ve bacteria and fungi.  相似文献   

17.
Structural Chemistry - The crystal structures of quaternary R3Fe0.5SnS7, R3Co0.5SnS7 and R3Ni0.5SnS7 (R = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy and Ho) compounds of La3Mn0.5SiS7 structure type (space...  相似文献   

18.
An anion-exchange procedure with 35% 3.5 N nitric acid-65% methanol as eiuant has been developed for the removal of Ce, Nd, Pr and La from Er, Dy, Gd, Eu and Sm, at the trace concentration level.  相似文献   

19.
Rare-earth hexaborides (RB6, R=Ce, Pr, Nd) nanocrystals were prepared by a facile solid state reaction in an autoclave. Single-crystalline RB6 nanocubes were fabricated at 500 °C starting from B2O3, RCl3·6H2O and Mg powder. RB6 nanoflakes and nanoparticles could be obtained around 400 °C using NaBH4 as boron resource. XRD patterns show that all of the hexaborides are cubic phase with high crystallinity and high purity and have lattice parameters that are consistent with nearly stoichiometric products. Raman spectra elucidate the active vibrational modes of the hexaborides. The TEM and FESEM images clearly show that the nanocubes have an average size of 200 nm and nanoparticles of 30 nm. Our experiment developed an efficient, simple and low-cost route to prepare RB6, which could be extended further to the preparation of other rare-earth metal hexaborides.  相似文献   

20.
The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.  相似文献   

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