cas 10035-01-5, YTTERBIUM(III) CHLORIDE HEXAHYDRATE

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The mononuclear and dinuclear dimethoxyethane adducts of lanthanide trichlorides [LnCl3(DME)2]n, n=1 or 2, fundamental starting materials in lanthanide chemistry: Preparation and structures
Some new dimethoxyethane (DME) adducts of lanthanide trichlorides of formula [LnCl3(DME)2]n, n=1 or 2; (n=2, Ln=La, Ce, Pr, Nd; n=1, Ln=Eu, Tb, Ho, Tm, Lu) have been prepared by treating Ln 2O3, or LnCl3·nH2O, or Ln2(CO3)3, in DME as medium, with thionyl chloride at room temperature, eventually in the presence of water in the case of Ln2O3 and Ln2(CO3)3. The complexes from lanthanum to praseodymium included are chloro-bridged dimers. In the case of neodymium, the new results complement the literature data, showing that both the mononuclear and dinuclear species exist: neodymium can therefore be regarded as the turning element from dinuclear to mononuclear structures along the series. Only mononuclear complexes were isolated in the Eu-Lu sequence. The lanthanide contraction has been evaluated on the basis of the Ln-O and Ln-Cl bond distances on the isotypical series of the mononuclear complexes LnCl3(DME)2 covering a range of 12 atomic numbers.
Baisch, Ulrich,Dell'Amico, Daniela Belli,Calderazzo, Fausto,Conti, Roberto,Labella, Luca,Marchetti, Fabio,Quadrelli, Elsje Alessandra
p. 1538 - 1548
(2004)
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Near-infrared luminescence from visible-light-sensitized hybrid materials covalently linked with tris(8-hydroxyquinolinate)-lanthanide [Er(III), Nd(III), and Yb(III)] derivatives
A series of new near-infrared (NIR) luminescent lanthanide-quinolinate derivatives [Ln(Q-Si)3] and xerogels (named as LnQSi-Gel, Ln = Er, Nd, Yb) covalently linked with the Ln(Q-Si)3 by using the 8-hydroxyquinoline-functionalized alkoxysilane (Q-Si) have been synthesized. The obtained xerogel materials LnQSi-Gel are rigid and show homogeneous by field-emission scanning electron microscopy (FE-SEM) images. The Fourier-transform infrared (FT-IR), fluorescence spectra of Ln(Q-Si) 3, and LnQSi-Gel were measured, and the corresponding luminescence decay analyses were recorded. Of importance here is that the excitation spectra of the Ln(Q-Si)3 and LnQSi-Gel extend to the region of visible light (more than 500 nm). Upon ligand-mediated excitation with the visible light, the Ln(Q-Si)3 and LnQSi-Gel show the characteristic NIR-luminescence of the corresponding lanthanide ions through the intramolecular energy transfer from the ligands to the lanthanide ions. The good luminescent performances enable these NIR-luminescent xerogel materials to have possible applications in medical diagnostics, laser systems, and optics, etc.
Sun, Lining,Dang, Song,Yu, Jiangbo,Feng, Jing,Shi, Liyi,Zhang, Hongjie
p. 16393 - 16397
(2010)
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Synthesis and characterization of new polynuclear lanthanide coordination polymers with 4,4′-oxybis(benzoic acid)
Three new polynuclear lanthanide coordination polymers [Ln 5(μ3-OH)(oba)7(H2O) 2]n ? 0.5nH2O (Ln = Eu (1), Ho (2)) and [Yb6(oba)9(H2O)]n (3) (H 2oba = 4,4′-oxybis(benzoic acid)), were prepared by hydrothermal reactions. 1 and 2 are isomorphous and exhibit complicated three-dimensional structures based on [Ln5(μ 3-OH)(oba)7(H2O)2] building blocks. In the asymmetric unit, there are five different coordination environments of Ln(III) ions, including a trinuclear hydroxo core. Complex 3 is a three-dimensional coordination polymer built up from a hexanuclear building block. In 3, Yb(III) ions have six different chemical environments and are in a regular arrangement, resulting in pseudohexagonal prisms along the a-axis. The luminescent property of 1 and magnetic behaviors of 2 and 3 have also been studied.
Wang, Yi-Bo,Sun, Chang-Yan,Zheng, Xiang-Jun,Gao, Song,Lu, Shao-Zhe,Jin, Lin-Pei
p. 823 - 830
(2005)
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Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles
Rare earth doped NaLa(WO4)2 nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu3+-doped NaLa(WO4)2 nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu3+-doped NaLa(WO4)2 nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er3+ and 20 mol% Yb3+ codoped NaLa(WO4)2 nanoparticles under 980 nm excitation could also be observed. The Yb3+-Er3+ codoped NaLa(WO4)2 nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.
Xue, Ning,Fan, Xianping,Wang, Zhiyu,Wang, Minquan
p. 1891 - 1896
(2008)
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Investigation of desolvation process in lanthanide dinicotinates
The desolvation process in lanthanide pyridine-3,5-dicarboxylates of the formulae [Tb2pdc3(dmf)2]?dmf (1), [Ho 2pdc3(dmf)2]?dmf (2), [Erdc 3(dmf)2]?dmf (3), and [Yb2pdc 3(dmf)2]?dmf (4) where pdc-C5H 3N(COO) 2 2-, dmf-N,N′-dimethylformamide) has been investigated by means of the TG-DSC, TG-FTIR, IR and XRD methods. Heating of the complexes in the range 30-260 °C lead to evolution of weakly bonded dmf molecules included in the channels as well those directly bonded with lanthanide atoms. The kinetic analysis revealed a multistep desolvation pattern.
Lyszczek,Iwan
p. 633 - 639
(2011)
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Synthesis, structure, thermal and luminescent behaviors of lanthanide-Pyridine-3,5-dicarboxylate frameworks series
The isostructural series of lanthanide pyridine-3,5-dicarboxylates of the formula [Ln2pdc3(dmf)2]·(dmf) x(H2O)y where Ln are lanthanides from La(III) to Lu(III); pdc2--C5/s
?yszczek, Renata
p. 120 - 127
(2011/01/08)

Synthesis, structure, and antibacterial properties of ternary rare-earth complexes with o-methylbenzoic Acid and 1,10-phenanthroline1
Ternary rare-earth complexes with o-methylbenzoic acid (o-MBA) and 1,10-phenanthroline (Phen) Ln2(o-MBA)6(Phen)2 ? nH2O(n = 0, 1) (Ln = La, Pr, Y, Yb) were synthesized and characterized by elemental analysis, IR
Chen,Wang,Yang,Zhao,Zhang,Wang,Zhao
p. 541 - 546
(2009/12/02)

Thermochemical properties of the rare earth complexes with pyromellitic acid
Fourteen rare earth complexes with pyromellitic acid were synthesized and characterized by means of chemical and elemental analysis, and TG-DTG. The constant-volume combustion energies of complexes, ΔcU, were measured by a precise rotating-bomb
Wang, Lijun,Liu, Fei,Yang, Xuwu,Wang, Xiaoyan,Liu, Ruiping,Zhao, Sa,Chen, Sanping
p. 43 - 46
(2009/05/30)

Solubility in the LaCl3-YbCl3-HCl-H2O system at 25°C
Solubility has been studied in the LaCl3-YbCl 3-HCl-H2O water-salt system at 25°C along the (40 ± 0.2)% HCl section; this is a eutonic-type system. The composition of the eutonic solution is as follows (wt %): LaCl3 ? 7H 2O, 4.67, YbCl3 ? 6H2O, 0.37; HCl, 37.98; and H2O, 56.98.
Knyazeva,Skiba,Voskoboinikov
p. 430 - 433
(2008/10/09)

Coordination polymers based on inorganic lanthanide(III) sulfate skeletons and an organic isonicotinate N-oxide connector: Segregation into three structural types by the lanthanide contraction effect
Fourteen three-dimensional coordination polymers of general formula [Ln(INO)(H2O)(SO4)]n, where Ln = La, 1·La; Ce, 2·Ce; Pr, 3·Pr; Nd, 4·Nd; Sm, 5·Sm; Eu, 6·Eu; Gd, 7·Gd; Tb, 8·Tb; Dy, 9·Dy; Ho, 10·Ho; Er, 11·Er; Tm, 12·Tm; Yb, 13·Yb; and Lu, 14·Lu; INO = isonicotinate-N-oxide, have been synthesized by hydrothermal reactions of Ln3+, MnCO3, MnSO4·H 2O, and isonicotinic acid N-oxide (HINO) at 155 °C and characterized by single-crystal X-ray diffraction, IR, thermal analysis, luminescence spectroscopy, and the magnetic measurement. The structures are formed by connection of layer, chain, or dimer of Ln-SO4 by the organic connector, INO. They belong to three structural types that are governed exclusively by the size of the ions: type I for the large ions, La, Ce, and Pr; type II for the medium ions, Nd, Sm, Eu, Gd, and Tb; and type III for the small ions, Dy, Ho, Er, Tm, Yb, and Lu. Type I consists of two-dimensional undulate Ln-sulfate layers pillared by INO to form a three-dimensional network. Type II has a 2-fold interpenetration of 3D herringbone networks, in which the catenation is sustained by extensive π-π interactions and O-H...O and C-H...O hydrogen bonds. Type III comprises one-dimensional chains that are connected by INO bridges, resulting in an α-Po network. The progressive structural change is due to the metal coordination number decreasing from nine for the large ions via eight to seven for the small ions, demonstrating clearly the effect of lanthanide contraction. The sulfate ion acts as a μ4- or μ3-bridge, connecting two, three, or four metals, and is both mono- and bidentate. The INO ligand acts as a μ3- or μ2-bridge with carboxylate group in syn-syn bridging or bidentate chelating mode. The materials show considerably high thermal stability. The magnetic properties of 4·Nd, 6·Eu, 7·Gd, and 13·Yb and the luminescence properties of 6·Eu and 8·Tb are also investigated.
He, Zheng,Gao, En-Qing,Wang, Zhe-Ming,Yan, Chun-Hua,Kurmoo, Mohamedally
p. 862 - 874
(2008/10/09)

Lanthanide complexes with 16- and 18-membered dibenzo-substituted macroheterocyclic ligands
The luminescence characteristics of Eu(III) and Yb(III) complexes with 16- and 18-membered dibenzo-substituted macroheterocyclic ligands were determined and their relationship with the complex composition was examined. It was shown that the low 4f luminescence intensity is caused by the inefficient excitation energy transfer from the triplet levels of the ligands to the resonance levels of the lanthanide ions. Copyright
Rusakova,Pavlovsky,Kulikov,Andronati,Korovin,Kost
p. 1516 - 1520
(2008/10/09)

Hydrothermal synthesis and structure of new lanthanide coordination polymers with dicarboxylic acid and 1,10-phenanthroline
[Ln(oba)(Hoba)(phen)]n (Ln=Er (1), Yb (2)) and [Er 2(bpndc)3(phen)]n (3) were obtained by hydrothermal reaction of LnCl3 with 4,4′-oxybis(benzoic acid) (H2oba), benzophenone-4, 4′-dicarboxylic acid (H 2bpndc) and 1,10-phenanthroline (phen), respectively, and characterized by single-crystal X-ray diffraction. The crystal structure reveals that 1 and 2 are isomorphous. In the asymmetric unit of 1 and 2, each Ln(III) center is eight-coordinated. 1D chains with two types of rings are formed by Ln(III)-O coordination bond, while 2D network and 3D supramolecular structures are built up by hydrogen bonds and π-π stacking, respectively. Complex 3 is a 3D structure composed of two crystallographically independent Er(III) atoms through bridging bpndc ligands.
Wang, Yibo,Wang, Zheming,Yan, Chunhua,Jin, Linpei
p. 177 - 186
(2007/10/03)

First Examples of Ternary Lanthanide 2,2′-Diphenyldicarboxylate Complexes: Hydrothermal Syntheses and Structures of Lanthanide Coordination Polymers of 2,2′-Diphenyldicarboxylic Acid and 1,10-Phenanthroline
In the four new lanthanide coordination polymers {[La 2(2,2′-dpdc)3(phen)(H2O)]·2H 2O)n (1), [Eu2(2,2′-dpdc) 3(phen)(H2-O)2]n (2), {[Ln 2(2,2′-dpdc)3(phen)2(H2O) 2]·4H2O},n [Ln = Tb (3), Yb (4)] (2,2′-dpdc = 2,2′-diphenyldicarboxylate, phen = 1,10-phenanthroline), prepared by hydrothermal synthesis, the 2,2′-dpdc dianion affords tetradentate, pentadentate, and hexadentate coordination modes. Complex 1 is a two-dimensional network of infinite 1-D chains assembled through π-π interactions, with nine- and ten-coordinate La3+, and arranged in wave-like layers. In 2, Eu3+ possesses nine- and ten-coordinate geometries bridged by 2,2′-dpdc ligands to give a 3-D structure. The isomorphous complexes 3 and 4, in which Tb3+ and Yb3+ ions are both nine-coordinate, have two-dimensional structures of 1-D zigzag chains stacked via hydrogen bonds and π-π interactions of phen molecules. The high-resolution emission spectrum of 2 shows two Eu 3+ ion sites, which is consistent with the results of the X-ray crystal structure analysis. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Wang, Yibo,Zheng, Xiangjun,Zhuang, Wenjuan,Jin, Linpei
p. 3572 - 3582
(2007/10/03)

Metal poly(benzimidazol-1-yl)borates. Synthesis and spectral characterization of some lanthanide chelates of hydridotris- and tetrakis(benzimidazol-1-yl)borate anions
Complexes of La(III), Nd(III), Pr(III), Sm(III), Tb(III), Dy(III), Ho(III), Er(III) and Yb(III) with hydridotris- and tetrakis(benzimidazol-1-yl) borate anions (L1 and L2) have been prepared and characterized. The spectral parameters β, b1/2, δ% and η, evaluated from the electronic spectra of the Pr, Nd, Sm, Ho and Er complexes, suggest the presence of a weak covalent contribution in the metal-ligand bond. The IR spectral data reveal that both L1 and L2 behave as tridentate ligands coordinating via the pyridyl and pyrrolic nitrogen atoms of the benzimidazolyl groups.
Khan, Tabrez A.,Khan, M. Arif,Khan,Haq
p. 297 - 308
(2008/10/08)

Hydrothermal synthesis and structural studies of novel 2-D lanthanide coordination polymers with phthalic acid
This paper presents four lanthanide coordination polymers, [Ln2(BDC)3(H2O)]n (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3; BDC = 1,2-benzenedicarboxylate) and [Yb4(BDC)6(H2O)2]n (4) prepared by the hydrothermal technique. They are all 2-D infinite structures with BDC anions connecting adjacent metal ions. In complex 1, La(III) ions are eight- and nine-coordinated, and all La(III) ions are coplanar in the 2-D structure. In complexes 2 and 3, Eu(III) and Tb(III) ions are also eight- and nine-coordinated, but they are distributed in a wave-like 2-D network. In complex 4, the Yb(III) ions have four different coordination numbers (6, 7, 8 and 9), which are rarely found in one lanthanide complex. Both the coordination numbers and the arrangement of Ln atoms in these coordination polymers show the lanthanide contraction. In the four complexes, all the oxygen atoms of BDC take part in coordination with Ln(III) ions, adopting tetra-, penta- and hexadentate coordination modes for the phthalate anions. The luminescent properties of complex 2 have been investigated and the results for the explanation of the chemical environment of the Eu(III) ion are consistent with the X-ray analysis.
Wan, Yonghong,Jin, Linpei,Wang, Kezhi,Zhang, Liping,Zhenga, Xiangjun,Lub, Shaozhe
p. 1590 - 1596
(2007/10/03)

Interaction of thulium, ytterbium(III) and lutetium chlorides with sodium chloride
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
p. 203 - 208
(2008/10/09)

Solution enthalpies of hydrates LnCl3·xH2O (Ln=Ce-Lu)
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
p. 1 - 7
(2008/10/09)

Ternary chlorides in the systems ACl/YbCl3 (A=Cs,Rb,K)
The phase diagrams of the ACl/YbCl3 (A=Cs,Rb,K) systems were investigated by DTA and XRD. Compounds A3YbCl6, A2YbCl5 and AYb2Cl7 exist in all systems, enneachlorides A3Yb2Cl9 in the systems with A=Cs,K. In the group AYb2Cl7, the Yb ions have coordination number 7, in all other compounds the coordination is octahedral. Thermodynamic functions determined by solution calorimetry and emf vs T measurements in galvanic cells for solid electrolytes reveal that the ternary chlorides AnYbCl3+n are stable compared with mixtures (nACl+YbCl3); the compounds Cs2YbCl5 and Rb2YbCl5 are stable only at temperatures >0 K.
Sebastian, J?rg,Seifert, Hans-Joachim
p. 29 - 37
(2008/10/09)

The dehydration schemes of rare-earth chlorides
The dehydration schemes of LaCl3·7H2O, CeCl3·7H2O, PrCl3·7H2O, PrCl3·7H2O, EuCl3·6H2O, GdCl3·OH2O, HoCl3·6H2O, ErCl3·OH2O, TmCl3·6H2O, YbCl3·OH2O and YCl3·6H2O have been investigated by the isothermal fluidizedbed technique. This technique is based on the fact that reactions proceed at a close approach to equilibrium and thus give rise to constant reaction rate regimes at constant gas flow and temperature in the bed. By injecting a small portion of HCl(g) (～1%) into the gas stream, hydrolysis is avoided, and dehydration to the monohydrate is recorded by both thermal analysis of the preheated inlet gas and chemical analysis of samples taken from the bed. Based on the present results, together with previous results on NdCl3·OH2O, TbCl3·6H2O and DyCl3·6H2O, dehydration schemes of all rare-earth chlorides except LuCl3 and ScCl3 are suggested.
Hong, Vu Van,Sundstroem, Johan
p. 37 - 43
(2008/10/09)

Orthorhombic low-temperature modifications of compounds Cs3LnCl6 (Ln = Nd-Yb)-preparation and thermodynamic stability
The compounds Cs3LnCl6 (Ln=Nd-Yb) can be obtained from aqueous solutions with an orthorhombic structure /S.G. Pbcm/, whereas from solutions in anhydrous acetic acid a modification with the monoclinic Cs3BiCl6 structure /S.G. C 2/c/ is formed. By solution calorimetry, the orthorhombic phase could be proved to be the low temperature modification. Molar volumes determined from X-ray powder patterns increase from Pbcm to C 2/c. The transition from the orthorhombic into the monoclinic phase is irreversible for kinetical reasons.
Reuter, Gert,Sebastian, J?rg,Roffe, Mark,Seifert, Hans-Joachim
p. 47 - 52
(2008/10/09)

SYNTHESIS AND SPECTRALINVESTIGATION ON RARE EARTH(III0 COMPLEXES OF AMIDO ACID LIGAND DERIVED FROM 2,4-DINITROPHENYLHYDRAZINE
Fourteen rare earth(III) complexes REL3.nH2O (where RE = Sc, n=5; Re = Z, La, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Zb, n = 6; RE = Pr, Nd, n =4; HL =1-(N-carboxymethyl-N-phenyl)amino-avetyl-2',4'-dinitrophenylhydrazine), have been synthesized and characterized
Shen, Xu,Xie, Yuyuan
p. 499 - 510
(2008/10/09)