Na 2EuAs 2S 5, NaEuAsS 4, and Na 4Eu(AsS 4) 2: Controlling the valency of arsenic in polysulfide fluxes

Tarun K. Bera; Mercouri G. Kanatzidis

doi:10.1021/ic202781c

Na ₂EuAs ₂S ₅, NaEuAsS ₄, and Na ₄Eu(AsS ₄) ₂: Controlling the valency of arsenic in polysulfide fluxes

Tarun K. Bera, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

The reactivity of europium with As species in Lewis basic alkali-metal polysulfide fluxes was investigated along with compound formation and the As ³⁺/As ⁵⁺ interplay vis-à-vis changes in the flux basicity. The compound Na ₂EuAs ₂S ₅ containing trivalent As ³⁺ is stabilized from an arsenic-rich polysulfide flux. It crystallizes in the monoclinic centrosymmetric space group P2 ₁/c. Na ₂EuAs ₂S ₅ has [As ₂S ₅] ^4- units, built of corner sharing AsS ₃ pyramids, which are coordinated to Eu ²⁺ ions to give a two-dimensional (2D) layered structure. A sodium polysulfide flux with comparatively less arsenic led to the As ⁵⁺ containing compounds NaEuAsS ₄ (orthorhombic, Ama2) and Na ₄Eu(AsS ₄) ₂ (triclinic, P1) depending on Na ₂S/S ratio. The NaEuAsS ₄ and Na ₄Eu(AsS ₄) ₂ have a three-dimensional (3D) structure built of [AsS ₄] ^3- tetrahedra coordinated to Eu ²⁺ ions. All compounds are semiconductors with optical energy gaps of ∼2 eV.

Original language	English (US)
Pages (from-to)	4293-4299
Number of pages	7
Journal	Inorganic chemistry
Volume	51
Issue number	7
DOIs	https://doi.org/10.1021/ic202781c
State	Published - Apr 2 2012

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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title = "Na 2EuAs 2S 5, NaEuAsS 4, and Na 4Eu(AsS 4) 2: Controlling the valency of arsenic in polysulfide fluxes",

abstract = "The reactivity of europium with As species in Lewis basic alkali-metal polysulfide fluxes was investigated along with compound formation and the As 3+/As 5+ interplay vis-{\`a}-vis changes in the flux basicity. The compound Na 2EuAs 2S 5 containing trivalent As 3+ is stabilized from an arsenic-rich polysulfide flux. It crystallizes in the monoclinic centrosymmetric space group P2 1/c. Na 2EuAs 2S 5 has [As 2S 5] 4- units, built of corner sharing AsS 3 pyramids, which are coordinated to Eu 2+ ions to give a two-dimensional (2D) layered structure. A sodium polysulfide flux with comparatively less arsenic led to the As 5+ containing compounds NaEuAsS 4 (orthorhombic, Ama2) and Na 4Eu(AsS 4) 2 (triclinic, P1) depending on Na 2S/S ratio. The NaEuAsS 4 and Na 4Eu(AsS 4) 2 have a three-dimensional (3D) structure built of [AsS 4] 3- tetrahedra coordinated to Eu 2+ ions. All compounds are semiconductors with optical energy gaps of ∼2 eV.",

author = "Bera, {Tarun K.} and Kanatzidis, {Mercouri G.}",

year = "2012",

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N2 - The reactivity of europium with As species in Lewis basic alkali-metal polysulfide fluxes was investigated along with compound formation and the As 3+/As 5+ interplay vis-à-vis changes in the flux basicity. The compound Na 2EuAs 2S 5 containing trivalent As 3+ is stabilized from an arsenic-rich polysulfide flux. It crystallizes in the monoclinic centrosymmetric space group P2 1/c. Na 2EuAs 2S 5 has [As 2S 5] 4- units, built of corner sharing AsS 3 pyramids, which are coordinated to Eu 2+ ions to give a two-dimensional (2D) layered structure. A sodium polysulfide flux with comparatively less arsenic led to the As 5+ containing compounds NaEuAsS 4 (orthorhombic, Ama2) and Na 4Eu(AsS 4) 2 (triclinic, P1) depending on Na 2S/S ratio. The NaEuAsS 4 and Na 4Eu(AsS 4) 2 have a three-dimensional (3D) structure built of [AsS 4] 3- tetrahedra coordinated to Eu 2+ ions. All compounds are semiconductors with optical energy gaps of ∼2 eV.

AB - The reactivity of europium with As species in Lewis basic alkali-metal polysulfide fluxes was investigated along with compound formation and the As 3+/As 5+ interplay vis-à-vis changes in the flux basicity. The compound Na 2EuAs 2S 5 containing trivalent As 3+ is stabilized from an arsenic-rich polysulfide flux. It crystallizes in the monoclinic centrosymmetric space group P2 1/c. Na 2EuAs 2S 5 has [As 2S 5] 4- units, built of corner sharing AsS 3 pyramids, which are coordinated to Eu 2+ ions to give a two-dimensional (2D) layered structure. A sodium polysulfide flux with comparatively less arsenic led to the As 5+ containing compounds NaEuAsS 4 (orthorhombic, Ama2) and Na 4Eu(AsS 4) 2 (triclinic, P1) depending on Na 2S/S ratio. The NaEuAsS 4 and Na 4Eu(AsS 4) 2 have a three-dimensional (3D) structure built of [AsS 4] 3- tetrahedra coordinated to Eu 2+ ions. All compounds are semiconductors with optical energy gaps of ∼2 eV.

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Na ₂EuAs ₂S ₅, NaEuAsS ₄, and Na ₄Eu(AsS ₄) ₂: Controlling the valency of arsenic in polysulfide fluxes

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