Cs3AgAs4Se8 and CsAgAs2Se4

Selenoarsenates with infinite 1(∞)[AsSe2]- chains in different Ag+ coordination environments

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Abstract

Two quaternary silver selenoarsenates Cs3AgAs4Se8 (I) and CsAgAs2Se4 (II) have been discovered by methanothermal reaction of Li3AsSe3 with AgBF4 in the presence of the respective alkali metal sources Cs2CO3 and CsCl. Orange crystals of Cs3AgAs4Se8 (I) were formed after reaction at 120 °C for 72 h, whereas red CsAgAs2Se4 (II) was obtained under slightly different conditions at 140 °C for 70 h. Both compounds possess novel two-dimensional (2D) polyanions consisting of infinite 1(∞)[AsSe2]- chains that are interconnected by Ag+ ions in different coordination patterns. In I, a double layer of 1(∞)[AsSe2]- chains is bridged by distorted trigonal planar coordinated Ag+ atoms to form a 2(∞)[AgAs4Se8]3- layer with a thickness of about 11.3 Å, The nonbonding Ag···Ag distances are about 4.220 Å, and large cavities within the layers accommodate for three of the four crystallographic Cs+ cations. The double amount of Ag+ atoms per AsSe2 chain unit in II leads to simple layers 2(∞)[AgAs2Se4]- {=[Ag2As4Se8]2-} in which the Ag+ atoms are arranged in rows between the 1(∞)[AsSe2]- chains, with alternating Ag···Ag distances of 3.053(3) and 3.488(3) Å. Hereby the 1(∞)[AsSe2]- polyanions show a disorder within the central (-As-Se(b))- chain (b = bridging), while the positions of the terminal Se atoms (Se(t)) remain unaffected. The thermal, optical, and spectroscopic properties of the compounds are reported. Both I and II melt with decomposition and are wide band gap semiconductors with values of 2.07 and 1.79 eV, respectively. Raman spectroscopic data show typical band patterns expected for infinite [AsSe2]- chains. Crystal Data: Cs3AgAs4Se8 (I), monoclinic, C2/c, a = 25.212(2) Å, b = 8.0748(7) Å, c = 22.803(2) Å, β = 116.272(2)°, Z = 8; CsAgAs2Se4 (II), monoclinic, P21/n, a = 10.9211(1) Å, b = 6.5188(2) Å, c = 13.7553(3) Å, β = 108.956(1)°, Z = 4.

Original languageEnglish
Pages (from-to)2337-2343
Number of pages7
JournalInorganic Chemistry
Volume39
Issue number11
DOIs
Publication statusPublished - May 29 2000

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Atoms
Alkali Metals
Crystals
atoms
Silver
Cations
Ions
Decomposition
alkali metals
crystals
thermodynamic properties
silver
disorders
broadband
decomposition
optical properties
cations
cavities
polyanions
ions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Cs3AgAs4Se8 and CsAgAs2Se4 : Selenoarsenates with infinite 1(∞)[AsSe2]- chains in different Ag+ coordination environments. / Wachhold, M.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 39, No. 11, 29.05.2000, p. 2337-2343.

Research output: Contribution to journalArticle

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title = "Cs3AgAs4Se8 and CsAgAs2Se4: Selenoarsenates with infinite 1(∞)[AsSe2]- chains in different Ag+ coordination environments",
abstract = "Two quaternary silver selenoarsenates Cs3AgAs4Se8 (I) and CsAgAs2Se4 (II) have been discovered by methanothermal reaction of Li3AsSe3 with AgBF4 in the presence of the respective alkali metal sources Cs2CO3 and CsCl. Orange crystals of Cs3AgAs4Se8 (I) were formed after reaction at 120 °C for 72 h, whereas red CsAgAs2Se4 (II) was obtained under slightly different conditions at 140 °C for 70 h. Both compounds possess novel two-dimensional (2D) polyanions consisting of infinite 1(∞)[AsSe2]- chains that are interconnected by Ag+ ions in different coordination patterns. In I, a double layer of 1(∞)[AsSe2]- chains is bridged by distorted trigonal planar coordinated Ag+ atoms to form a 2(∞)[AgAs4Se8]3- layer with a thickness of about 11.3 {\AA}, The nonbonding Ag···Ag distances are about 4.220 {\AA}, and large cavities within the layers accommodate for three of the four crystallographic Cs+ cations. The double amount of Ag+ atoms per AsSe2 chain unit in II leads to simple layers 2(∞)[AgAs2Se4]- {=[Ag2As4Se8]2-} in which the Ag+ atoms are arranged in rows between the 1(∞)[AsSe2]- chains, with alternating Ag···Ag distances of 3.053(3) and 3.488(3) {\AA}. Hereby the 1(∞)[AsSe2]- polyanions show a disorder within the central (-As-Se(b))- chain (b = bridging), while the positions of the terminal Se atoms (Se(t)) remain unaffected. The thermal, optical, and spectroscopic properties of the compounds are reported. Both I and II melt with decomposition and are wide band gap semiconductors with values of 2.07 and 1.79 eV, respectively. Raman spectroscopic data show typical band patterns expected for infinite [AsSe2]- chains. Crystal Data: Cs3AgAs4Se8 (I), monoclinic, C2/c, a = 25.212(2) {\AA}, b = 8.0748(7) {\AA}, c = 22.803(2) {\AA}, β = 116.272(2)°, Z = 8; CsAgAs2Se4 (II), monoclinic, P21/n, a = 10.9211(1) {\AA}, b = 6.5188(2) {\AA}, c = 13.7553(3) {\AA}, β = 108.956(1)°, Z = 4.",
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T1 - Cs3AgAs4Se8 and CsAgAs2Se4

T2 - Selenoarsenates with infinite 1(∞)[AsSe2]- chains in different Ag+ coordination environments

AU - Wachhold, M.

AU - Kanatzidis, Mercouri G

PY - 2000/5/29

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N2 - Two quaternary silver selenoarsenates Cs3AgAs4Se8 (I) and CsAgAs2Se4 (II) have been discovered by methanothermal reaction of Li3AsSe3 with AgBF4 in the presence of the respective alkali metal sources Cs2CO3 and CsCl. Orange crystals of Cs3AgAs4Se8 (I) were formed after reaction at 120 °C for 72 h, whereas red CsAgAs2Se4 (II) was obtained under slightly different conditions at 140 °C for 70 h. Both compounds possess novel two-dimensional (2D) polyanions consisting of infinite 1(∞)[AsSe2]- chains that are interconnected by Ag+ ions in different coordination patterns. In I, a double layer of 1(∞)[AsSe2]- chains is bridged by distorted trigonal planar coordinated Ag+ atoms to form a 2(∞)[AgAs4Se8]3- layer with a thickness of about 11.3 Å, The nonbonding Ag···Ag distances are about 4.220 Å, and large cavities within the layers accommodate for three of the four crystallographic Cs+ cations. The double amount of Ag+ atoms per AsSe2 chain unit in II leads to simple layers 2(∞)[AgAs2Se4]- {=[Ag2As4Se8]2-} in which the Ag+ atoms are arranged in rows between the 1(∞)[AsSe2]- chains, with alternating Ag···Ag distances of 3.053(3) and 3.488(3) Å. Hereby the 1(∞)[AsSe2]- polyanions show a disorder within the central (-As-Se(b))- chain (b = bridging), while the positions of the terminal Se atoms (Se(t)) remain unaffected. The thermal, optical, and spectroscopic properties of the compounds are reported. Both I and II melt with decomposition and are wide band gap semiconductors with values of 2.07 and 1.79 eV, respectively. Raman spectroscopic data show typical band patterns expected for infinite [AsSe2]- chains. Crystal Data: Cs3AgAs4Se8 (I), monoclinic, C2/c, a = 25.212(2) Å, b = 8.0748(7) Å, c = 22.803(2) Å, β = 116.272(2)°, Z = 8; CsAgAs2Se4 (II), monoclinic, P21/n, a = 10.9211(1) Å, b = 6.5188(2) Å, c = 13.7553(3) Å, β = 108.956(1)°, Z = 4.

AB - Two quaternary silver selenoarsenates Cs3AgAs4Se8 (I) and CsAgAs2Se4 (II) have been discovered by methanothermal reaction of Li3AsSe3 with AgBF4 in the presence of the respective alkali metal sources Cs2CO3 and CsCl. Orange crystals of Cs3AgAs4Se8 (I) were formed after reaction at 120 °C for 72 h, whereas red CsAgAs2Se4 (II) was obtained under slightly different conditions at 140 °C for 70 h. Both compounds possess novel two-dimensional (2D) polyanions consisting of infinite 1(∞)[AsSe2]- chains that are interconnected by Ag+ ions in different coordination patterns. In I, a double layer of 1(∞)[AsSe2]- chains is bridged by distorted trigonal planar coordinated Ag+ atoms to form a 2(∞)[AgAs4Se8]3- layer with a thickness of about 11.3 Å, The nonbonding Ag···Ag distances are about 4.220 Å, and large cavities within the layers accommodate for three of the four crystallographic Cs+ cations. The double amount of Ag+ atoms per AsSe2 chain unit in II leads to simple layers 2(∞)[AgAs2Se4]- {=[Ag2As4Se8]2-} in which the Ag+ atoms are arranged in rows between the 1(∞)[AsSe2]- chains, with alternating Ag···Ag distances of 3.053(3) and 3.488(3) Å. Hereby the 1(∞)[AsSe2]- polyanions show a disorder within the central (-As-Se(b))- chain (b = bridging), while the positions of the terminal Se atoms (Se(t)) remain unaffected. The thermal, optical, and spectroscopic properties of the compounds are reported. Both I and II melt with decomposition and are wide band gap semiconductors with values of 2.07 and 1.79 eV, respectively. Raman spectroscopic data show typical band patterns expected for infinite [AsSe2]- chains. Crystal Data: Cs3AgAs4Se8 (I), monoclinic, C2/c, a = 25.212(2) Å, b = 8.0748(7) Å, c = 22.803(2) Å, β = 116.272(2)°, Z = 8; CsAgAs2Se4 (II), monoclinic, P21/n, a = 10.9211(1) Å, b = 6.5188(2) Å, c = 13.7553(3) Å, β = 108.956(1)°, Z = 4.

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