- New Metal-Rich Erbium Iodides with Condensed Clusters: Er7I10 and Er4I5.
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The compounds Er//4I//5 and Er//7I//1//0 are formed as single crystals by reacting ErI//3 and erbium in sealed tantalum capsules at temperatures between 1000 and 1200 degree C. Both compounds crystallize in the monoclinic system. The structures contain on
- Berroth,Simon
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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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- Rare-earth iodides in ionic liquids: Crystal structures of [bmpyr]4[LnI6][Tf2N] (Ln = La, Er)
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Deliberately designed ionic liquids can be excellent solvents for organic reactions with lanthanide compounds, e.g. Lewis catalysis with trivalent lanthanides. Little is known about the solvation and complexation of these Lewis-acid catalysts in these-still uncommon-solvents, although the knowledge of these processes is a prerequisite for a basic understanding of reaction mechanisms and catalytic cycles. Therefore, we have investigated the chemical behaviour of rare-earth metal iodides in the ionic liquid [bmpyr][Tf2N] (bmpyr = 1,1-n-butyl-methylpyrrolidinium; Tf2N = bis(trifluoromethanesulfonyl)-amide). Compounds of the general composition [bmpyr]4[LnI6][Tf2N] could be crystallized from solutions of LnI3 (Ln = La, Er), in [bmpyr][Tf2N]. Single-crystal X-ray diffraction data show that the trivalent rare-earth cations are octahedrally coordinated by six iodide anions. Eight cations of the ionic liquid are located tangentially above each of the triangular faces of the [LnI6] octahedron. According to the size of the trivalent cation, the crystal structure adjusts itself by tilting of the [LnI6] octahedra to accommodate one anion of the ionic liquid, bis(trifluoromethanesulfonyl)-amide, which completes the crystal structure of the composition [bmpyr]4[LnI6][Tf2N].
- Babai, Arash,Mudring, Anja-Verena
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p. 122 - 127
(2008/10/09)
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- Intense near-infrared luminescence of anhydrous lanthanide(III) iodides in an imidazolium ionic liquid
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Anhydrous neodymium(III) iodide and erbium(III) iodide were dissolved in carefully dried batches of the ionic liquid 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C12mim][Tf2N]. Provided that the ionic liquid had a low water content, intense near-infrared emission could be observed for both the neodymium(III) ion and for the erbium(III) ion. Luminescence lifetimes have been measured, and the quantum yield of the neodymium(III) sample has been measured. Exposure of the hygroscopic samples to atmospheric moisture conditions caused a rapid decrease of the luminescence intensities.
- Arenz, Sven,Babai, Arash,Binnemans, Koen,Driesen, Kris,Giernoth, Ralf,Mudring, Anja-Verena,Nockemann, Peter
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- On the reactivity of lanthanide iodides LnIx (x < 3) formed in the reactions of lanthanide metals with iodine
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The reduced lanthanide iodides of the composition LnIx (Ln = Sc, Y, La, Ce, Pr, Gd, Ho, and Er; x 3) were obtained by the reaction of an excess of the appropriate metal with iodine at high temperatures. The diamagnetism of the Sc, Y, and La d
- Khoroshenkov,Petrovskaya,Fedushkin,Bochkarev
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p. 699 - 702
(2008/10/08)
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- Rare earth iodide complexes of 4-formyl-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one
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Rare earth complexes of 4-formyl-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (FDPP) having the general formula [Ln(FDPP)4I2]I, where Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho and Er, have been synthesised and characterised by elemental analyses, molar conductance in non-aqueous solvents, electronic, infrared and proton NMR spectra as well as thermogravimetric analyses. FDPP acts as a neutral monodentate ligand coordinating through the ring carbonyl oxygen. Two of the iodide ions are coordinated. A coordination number of six may be assigned to the metal ion in these complexes. The covalency parameters evaluated from the solid state electronic spectra suggest weak covalent character of the metal-ligand bond. The TG data of the lanthanum complex indicate that the complex is stable up to about 140° C and undergoes decomposition in three stages forming lanthanum oxide as the final product.
- Joseph, Siby,Radhakrishnan
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p. 1219 - 1229
(2008/10/09)
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- Thermal Constants of Melting for Erbium Iodide
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Samples of ErI3 are prepared by iodination of erbium metal by iodine vapor and identified by chemical and X-ray diffraction analyses. The melting point [Tm1(ErI3) = 1282 ± 10 K] and the enthalpy of melting [ΔmH0(ErI3) = 29.7 ± 3.0 kJ/mol] are determined by DTA; the entropy of melting is calculated: ΔmS0(ErI3) = 23 ± 3 J/(mol K).
- Goryuskin,Poshevneva,Vinokurova
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p. 1029 - 1030
(2008/10/08)
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- The crystal structures of ErSeI and NaErSe2
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It is reported about attempts to synthesize lanthanoide selenidehalides of the formula LnSeX (X = Cl, Br, I) exemplary for Ln = Er. The relative stabilities of these compounds are discussed. X-ray crystal structure analysis revealed for the compounds ErSeBr and ErSeI the FeOCl-structure type (space group Pmmn, Z = 2, a = 406.3(5) pm, b = 559.2(6) pm, and c = 795(1) pm, and a = 418.26(6) pm, b = 558.4(1) pm. and c = 889.0(2) pm, respectively). A corresponding chloride was not found within the scope of this investigation. From the educts Er2Se3 and ErCl3 in the presence of NaCl as flux in Nb-ampoules the compound NaErSe2 was formed instead which crystallines in an α-NaFeO2-type structure (space group R3?m, Z = 3, a = 408.41(2) pm and c = 2067.4(2) pm).
- St?we
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p. 1639 - 1643
(2008/10/09)
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