The Thermal Dehydration of Cs3LnCl6 · 3H2O to Cs3LnCl6 (Ln = La-Nd) and Their Crystal Structures

Reuter, G.; Frenzen, G.

doi:10.1006/jssc.1995.1222

Cited by 22 publications

(11 citation statements)

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“…Based on a literature survey, it seems that the fitted Ln–Cl distances for Nd and Eu correlate quite well with CN’s of six and five, respectively (Table S13). − This is much lower than the fitted CN of 10 for both lanthanides. Homoleptic Nd 3+ - and Eu 3+ -chloro complexes tend to be six-coordinate octahedra, with average Ln–Cl distances of 2.73 and 2.69 Å, respectively.…”

Section: Results and Discussionmentioning

confidence: 81%

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

et al. 2021

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Deep eutectic solvents are a new class of green solvents that are being explored as an alternative for used nuclear fuel and critical material recycling. However, there is a paucity of knowledge regarding metal behavior in them. This paper explores the underlying chemistry of rare-earth elements in choline chloride-based deep eutectic solvents by using a multi-technique spectroscopic methodology. Results show that speciation is highly dependent on the choice of the hydrogen-bond donor. Collected EXAFS data showed Ln 3+ coordination with ethylene glycol and urea in their respective solvents and coordination with chloride in the lactic acid system. Generalized coordination environments were determined to be [LnL 4–5 ], [LnL 7–10 ], and [LnL 5–6 ] in the ethylene glycol, urea, and lactic acid systems, respectively. Collected UV/vis spectra for Nd 3+ and Er 3+ showed variations with changing solvents, showing that Ln–Cl interactions do not dominate in these systems. Luminescence studies were consistent, showing varying emission spectra with varying solvent systems. The shortest luminescent lifetimes were observed in the choline chloride–ethylene glycol deep eutectic solvent, suggesting coordination through O–H groups. Combining all collected data allowed Eu 3+ coordination geometries to be assigned.

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Section: Results and Discussionmentioning

confidence: 81%

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

et al. 2021

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“…[5] The lattice parameters of oP-Rb 3 BiBr 6 • 1 = 2 H 2 O are even somewhat smaller than those reported for Rb 3 BiBr 6 by Lazarini in 1978. [16] The densities of oP-and mP-Rb While tP-Cs 3 BiBr 6 has a distinct structure (Figure 2), the other four structures are polytypes, i. e. they consist of the same two [15] ) at 293 K (Cs 3 NdCl 6 type [24] )…”

Section: Crystal Structuresmentioning

confidence: 99%

“…at 296 K (Cs 3 NdCl 6 type [24] ) types of alternating layers but differ in stacking sequence (Figure 3). Their asymmetric units, including the displacement parameters of the atoms, are very similar (Figures S9 and S10).…”

Section: Crystal Structuresmentioning

confidence: 99%

The Polymorphic Nature of M₃BiBr₆ Halides (M=Cs, Rb) and their Reversible Intercalation with Water to Isomorphous Hydrates at Room Temperature

Chang

Doert

Ruck

2021

Zeitschrift anorg allge chemie

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Bismuthates with composition M3BiBr6 (M=Rb, Cs) form series of polymorphs capable of reversible H2O incorporation at room temperature. The host compounds were synthesized by annealing mixtures of MBr/BiBr3, or by precipitation from acidic solution and removing water molecules from the host framework of the hydrates in a thermal dehydration reaction. While the compound oP‐Rb3BiBr6 (space group Pbnm) is known from previous work, mP‐Rb3BiBr6 crystallizes with a new type of structure (space group P21/c). For Cs3BiBr6, the oP‐phase crystallizes isostructural to Cs3NdCl6 (space group Pbcm), the mC‐phase isostructural to Cs3BiCl6 (space group C2/c) and the tP‐phase isostructural to Tl3BiCl6 (space group P42/m). All crystal structures were refined from single crystal X‐ray diffraction data. In both systems, the crystal structures of orthorhombic and the monoclinic phases are polytypes and differ by stacking sequence only. By intercalation of water molecules, all polytypes of M3BiBr6 transform to semi‐hydrates M3BiBr6 ⋅ 1/2 H2O. Both, the incorporation of water and the reverse process proceed without the host structure being changed. The inclusion of crystal water was also confirmed by IR‐spectroscopy, thermal gravimetric analysis and mass spectrometry. The modification tP‐Cs3BiBr6 features a crystal structure with higher density and does not accommodate water.

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“…Recently, we found a new distortional variant of the cubic elpasolite structure for Cs3NdC16 (Reuter & Frenzen, 1995) and have since shown that this low-temperature phase occurs for all lanthanides from Nd to Yb (Reuter, Roffe & Seifert, 1996). Apart from the 3:1, 2:1 and 1:2 compounds, an enneachloride Cs3Ln2C19 exists for Ln = Ho, Tm, Yb and Lu (Meyer & Sch6nemund, 1980).…”

Section: Commentmentioning

confidence: 99%

Tetracaesium Ytterbium Heptachloride with Partly Disordered Chloride Ions

Reuter¹,

Sebastian²,

Frenzen³

1996

Acta Crystallogr C

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The Thermal Dehydration of Cs3LnCl6 · 3H2O to Cs3LnCl6 (Ln = La-Nd) and Their Crystal Structures

Cited by 22 publications

References 0 publications

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

The Polymorphic Nature of M₃BiBr₆ Halides (M=Cs, Rb) and their Reversible Intercalation with Water to Isomorphous Hydrates at Room Temperature

Tetracaesium Ytterbium Heptachloride with Partly Disordered Chloride Ions

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The Thermal Dehydration of Cs3LnCl6 · 3H2O to Cs3LnCl6 (Ln = La-Nd) and Their Crystal Structures

Cited by 22 publications

References 0 publications

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

The Polymorphic Nature of M3BiBr6 Halides (M=Cs, Rb) and their Reversible Intercalation with Water to Isomorphous Hydrates at Room Temperature

Tetracaesium Ytterbium Heptachloride with Partly Disordered Chloride Ions

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The Polymorphic Nature of M₃BiBr₆ Halides (M=Cs, Rb) and their Reversible Intercalation with Water to Isomorphous Hydrates at Room Temperature