ChemInform Abstract: Detection and Structural Study of a New Family of Layered Compounds of the General Composition (UO)2RS3 (R: Gd to Lu and Y).

Guittard, M.; Vovan, T.; Julien‐Pouzol, M.; Jaulmes, S.; Laruelle, P.; Flahaut, Jean

doi:10.1002/chin.198707035

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“…One such group of quaternary chalcogenides belongs to the hexagonal crystal system space group P6 3 , first reported in 1968 as the cell parameters calculated from powder X-ray diffraction data, and has proven to be a remarkably robust structure type. 8 Single-crystal structure investigations revealed that these compounds belong to the Ce 6 Al 3.33 S 14 9 or La 3 CuSiS 7 structure type. 10 Today, a large number of compounds are known with this structure type with the general formula A 6 B 2 C 2 Q 14 or A 3 BCQ 7 , while some have vacancies within the [A−B] metal network.…”

Section: ■ Introductionmentioning

confidence: 99%

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La₃CuSiS₇ Structure Type

Choudhury

Dorhout

2014

Inorg. Chem.

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Five new isotypic quaternary chalcogenides containing rare-earth metal atoms crystallizing in the hexagonal noncentrosymmetric space group P6(3) (No. 173) with the La(3)CuSiS(7) structure type have been synthesized by reacting the appropriate anhydrous rare-earth trichloride with sodium thiogermanate, Na(2)GeS(3). The reaction between LnCl(3) and Na(2)GeS(3) in an evacuated fused-silica ampule produced high yields of good-quality crystals of NaLn(3)GeS(7) [Ln = Ce (I), Nd (II), Sm (III), Gd (IV), and Yb (V)], while a similar reaction between EuCl(3) and Na(2)GeS(3) yielded a quinary chloride thiogermanate, Na(1.2)Eu(3.4)Cl(2)Ge(3)S(9) (VI), incorporating a cyclic trimeric Ge(3)S(9) building unit and adopting a structure related to La(3)CuSiS(7). The crystal structure of the compounds comprises a complex network of bicapped trigonal-prismatic LnS(8) and GeS(4) tetrahedra, which creates channels along the [001] direction. The Na(+) cations reside in these channels within trigonally distorted octahedral coordination environments, surrounded by six S atoms. For compounds III-V, the temperature dependence of the magnetic susceptibility indicates that these compounds are paramagnetic with μ(eff). = 1.86, 8.01, and 3.87 μ(B), for III-V, respectively. The experimental μ(eff) for IV is close to the theoretical value of 7.94 for free Gd(3+) ions, while μ(eff) values for III and V deviate from their theoretical values of 0.86 and 4.54 μ(B) for Sm(3+) and Yb(3+) ions, respectively. These compounds are semiconductors with optical band gaps of around 1.3 eV for III and V. Extended Hückel calculations suggest that the valence band comprises primarily S 3p and the bottom of the conduction band is dominated by empty rare-earth 5d orbitals. Compound VI exhibits a sharp optical absorption of around 2.18 eV, which is attributed to the f → d transition of Eu(II). The effective magnetic moment of 7.94 μ(B)/Eu is in excellent agreement with the theoretical value of 7.94 μ(B) for the free Eu(2+) ion.

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Section: ■ Introductionmentioning

confidence: 99%

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La₃CuSiS₇ Structure Type

Choudhury

Dorhout

2014

Inorg. Chem.

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ChemInform Abstract: Detection and Structural Study of a New Family of Layered Compounds of the General Composition (UO)2RS3 (R: Gd to Lu and Y).

Cited by 1 publication

References 1 publication

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La₃CuSiS₇ Structure Type

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La₃CuSiS₇ Structure Type

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ChemInform Abstract: Detection and Structural Study of a New Family of Layered Compounds of the General Composition (UO)2RS3 (R: Gd to Lu and Y).

Cited by 1 publication

References 1 publication

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La3CuSiS7 Structure Type

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La3CuSiS7 Structure Type

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Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La₃CuSiS₇ Structure Type

Alkali-Metal Thiogermanates: Sodium Channels and Variations on the La₃CuSiS₇ Structure Type