Impressive Structural Diversity and Polymorphism in the Modular Compounds ABi3Q5 (A = Rb, Cs; Q = S, Se, Te)

Lykourgos Iordanidis, Daniel Bilc, Subhendra D. Mahanti, Mercouri G Kanatzidis

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Abstract

An outstanding example of structural diversity and complexity is found in the compounds with the general formula ABi3Q5 (A = alkali metal; Q = chalcogen). γ-RbBi3S5 (I), α-RbBi3Se5 (II), β-RbBi3Se 5 (III), γ-RbBi3Se5 (IV), CsBi 3Se5 (V), RbBi3Se4Te (VI), and RbBi3Se3Te2 (VII) were synthesized from A 2Q (A = Rb, Cs; Q = S, Se) and Bi2Q3 (Q = S, Se or Te) at temperatures above 650 °C using appropriate reaction protocols. γ-RbBi3S5 and α-RbBi3Se 5 have three-dimensional tunnel structures while the rest of the compounds have lamellar structures. γ-RbBi3S5, γ-RbBi3S5, and its isostructural analogues RbBi 3Se4Te and RbBi3Se3Te2 crystallize in the orthorhombic space group Pnma with a = 11.744(2) Å, b = 4.0519(5) Å, c = 21.081(3) Å, R1 = 2.9%, wR2 = 6.3% for (I), a = 21.956(7) Å, b = 4.136(2) Å, c = 12.357(4), Å, R1 = 6.2%, wR2 = 13.5% for (IV), and a = 22.018(3), Å, b = 4.2217(6), Å, c = 12.614(2) Å, R1 = 6.2%, wR2 = 10.3% for (VI). γ-RbBi 3S5 has a three-dimensional tunnel structure that differs from the Se analogues, α-RbBi3Se5 crystallizes in the monoclinic space group C2/m with a = 36.779(4) Å, b = 4.1480(5), Å, c = 25.363(3), Å, β = 120.403(2)o, R1 = 4.9%, wR2 = 9.9%. β-RbBi3Se5 and isostructural CsBi3Se 5 adopt the space group P21/m with a = 13.537(2), Å, b = 4.1431(6), Å, c = 21.545(3) Å, β = 91.297(3)°, R1 = 4.9%, wR2 = 11.0% for (III) and a = 13.603(3), Å, b = 4.1502(8) Å, c = 21.639(4), Å, β = 91.435(3)°, R1 = 6.1%, wR2 = 13.4% for (V). α-RbBi3Se5 is also three-dimensional, whereas β-RbBi3Se5 and CsBi3Se5 have stepped layers with alkali metal ions found disordered in several trigonal prismatic sites between the layers. In γ-RbBi3Se5 and RbBi3Se4Te, the layers consist of Bi 2Te3-type fragments, which are connected in a stepwise manner. In the mixed Se/Te analogue, the Te occupies the chalcogen sites that are on the "surface" of the layers. All compounds are narrow band-gap semiconductors with optical band gaps ranging 0.4-1.0 eV. The thermal stability of all phases was studied, and it was determined that γ-RbBi 3Se5 is more stable than the and α- and β-forms. Electronic band calculations at the density functional theory (DFT) level performed on α-, β-, and γ-RbBi3Se 5 support the presence of indirect band gaps and were used to assess their relative thermodynamic stability.

Original languageEnglish
Pages (from-to)13741-13752
Number of pages12
JournalJournal of the American Chemical Society
Volume125
Issue number45
DOIs
Publication statusPublished - Nov 12 2003

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Chalcogens
Alkali Metals
Alkali metals
Polymorphism
Tunnels
Thermodynamic stability
Semiconductors
Lamellar structures
Optical band gaps
Thermodynamics
Density functional theory
Metal ions
Energy gap
Hot Temperature
Ions
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

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Impressive Structural Diversity and Polymorphism in the Modular Compounds ABi3Q5 (A = Rb, Cs; Q = S, Se, Te). / Iordanidis, Lykourgos; Bilc, Daniel; Mahanti, Subhendra D.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 125, No. 45, 12.11.2003, p. 13741-13752.

Research output: Contribution to journalArticle

@article{77a1da518e0442fcbfcdf8879595154c,
title = "Impressive Structural Diversity and Polymorphism in the Modular Compounds ABi3Q5 (A = Rb, Cs; Q = S, Se, Te)",
abstract = "An outstanding example of structural diversity and complexity is found in the compounds with the general formula ABi3Q5 (A = alkali metal; Q = chalcogen). γ-RbBi3S5 (I), α-RbBi3Se5 (II), β-RbBi3Se 5 (III), γ-RbBi3Se5 (IV), CsBi 3Se5 (V), RbBi3Se4Te (VI), and RbBi3Se3Te2 (VII) were synthesized from A 2Q (A = Rb, Cs; Q = S, Se) and Bi2Q3 (Q = S, Se or Te) at temperatures above 650 °C using appropriate reaction protocols. γ-RbBi3S5 and α-RbBi3Se 5 have three-dimensional tunnel structures while the rest of the compounds have lamellar structures. γ-RbBi3S5, γ-RbBi3S5, and its isostructural analogues RbBi 3Se4Te and RbBi3Se3Te2 crystallize in the orthorhombic space group Pnma with a = 11.744(2) {\AA}, b = 4.0519(5) {\AA}, c = 21.081(3) {\AA}, R1 = 2.9{\%}, wR2 = 6.3{\%} for (I), a = 21.956(7) {\AA}, b = 4.136(2) {\AA}, c = 12.357(4), {\AA}, R1 = 6.2{\%}, wR2 = 13.5{\%} for (IV), and a = 22.018(3), {\AA}, b = 4.2217(6), {\AA}, c = 12.614(2) {\AA}, R1 = 6.2{\%}, wR2 = 10.3{\%} for (VI). γ-RbBi 3S5 has a three-dimensional tunnel structure that differs from the Se analogues, α-RbBi3Se5 crystallizes in the monoclinic space group C2/m with a = 36.779(4) {\AA}, b = 4.1480(5), {\AA}, c = 25.363(3), {\AA}, β = 120.403(2)o, R1 = 4.9{\%}, wR2 = 9.9{\%}. β-RbBi3Se5 and isostructural CsBi3Se 5 adopt the space group P21/m with a = 13.537(2), {\AA}, b = 4.1431(6), {\AA}, c = 21.545(3) {\AA}, β = 91.297(3)°, R1 = 4.9{\%}, wR2 = 11.0{\%} for (III) and a = 13.603(3), {\AA}, b = 4.1502(8) {\AA}, c = 21.639(4), {\AA}, β = 91.435(3)°, R1 = 6.1{\%}, wR2 = 13.4{\%} for (V). α-RbBi3Se5 is also three-dimensional, whereas β-RbBi3Se5 and CsBi3Se5 have stepped layers with alkali metal ions found disordered in several trigonal prismatic sites between the layers. In γ-RbBi3Se5 and RbBi3Se4Te, the layers consist of Bi 2Te3-type fragments, which are connected in a stepwise manner. In the mixed Se/Te analogue, the Te occupies the chalcogen sites that are on the {"}surface{"} of the layers. All compounds are narrow band-gap semiconductors with optical band gaps ranging 0.4-1.0 eV. The thermal stability of all phases was studied, and it was determined that γ-RbBi 3Se5 is more stable than the and α- and β-forms. Electronic band calculations at the density functional theory (DFT) level performed on α-, β-, and γ-RbBi3Se 5 support the presence of indirect band gaps and were used to assess their relative thermodynamic stability.",
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T1 - Impressive Structural Diversity and Polymorphism in the Modular Compounds ABi3Q5 (A = Rb, Cs; Q = S, Se, Te)

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AU - Mahanti, Subhendra D.

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N2 - An outstanding example of structural diversity and complexity is found in the compounds with the general formula ABi3Q5 (A = alkali metal; Q = chalcogen). γ-RbBi3S5 (I), α-RbBi3Se5 (II), β-RbBi3Se 5 (III), γ-RbBi3Se5 (IV), CsBi 3Se5 (V), RbBi3Se4Te (VI), and RbBi3Se3Te2 (VII) were synthesized from A 2Q (A = Rb, Cs; Q = S, Se) and Bi2Q3 (Q = S, Se or Te) at temperatures above 650 °C using appropriate reaction protocols. γ-RbBi3S5 and α-RbBi3Se 5 have three-dimensional tunnel structures while the rest of the compounds have lamellar structures. γ-RbBi3S5, γ-RbBi3S5, and its isostructural analogues RbBi 3Se4Te and RbBi3Se3Te2 crystallize in the orthorhombic space group Pnma with a = 11.744(2) Å, b = 4.0519(5) Å, c = 21.081(3) Å, R1 = 2.9%, wR2 = 6.3% for (I), a = 21.956(7) Å, b = 4.136(2) Å, c = 12.357(4), Å, R1 = 6.2%, wR2 = 13.5% for (IV), and a = 22.018(3), Å, b = 4.2217(6), Å, c = 12.614(2) Å, R1 = 6.2%, wR2 = 10.3% for (VI). γ-RbBi 3S5 has a three-dimensional tunnel structure that differs from the Se analogues, α-RbBi3Se5 crystallizes in the monoclinic space group C2/m with a = 36.779(4) Å, b = 4.1480(5), Å, c = 25.363(3), Å, β = 120.403(2)o, R1 = 4.9%, wR2 = 9.9%. β-RbBi3Se5 and isostructural CsBi3Se 5 adopt the space group P21/m with a = 13.537(2), Å, b = 4.1431(6), Å, c = 21.545(3) Å, β = 91.297(3)°, R1 = 4.9%, wR2 = 11.0% for (III) and a = 13.603(3), Å, b = 4.1502(8) Å, c = 21.639(4), Å, β = 91.435(3)°, R1 = 6.1%, wR2 = 13.4% for (V). α-RbBi3Se5 is also three-dimensional, whereas β-RbBi3Se5 and CsBi3Se5 have stepped layers with alkali metal ions found disordered in several trigonal prismatic sites between the layers. In γ-RbBi3Se5 and RbBi3Se4Te, the layers consist of Bi 2Te3-type fragments, which are connected in a stepwise manner. In the mixed Se/Te analogue, the Te occupies the chalcogen sites that are on the "surface" of the layers. All compounds are narrow band-gap semiconductors with optical band gaps ranging 0.4-1.0 eV. The thermal stability of all phases was studied, and it was determined that γ-RbBi 3Se5 is more stable than the and α- and β-forms. Electronic band calculations at the density functional theory (DFT) level performed on α-, β-, and γ-RbBi3Se 5 support the presence of indirect band gaps and were used to assess their relative thermodynamic stability.

AB - An outstanding example of structural diversity and complexity is found in the compounds with the general formula ABi3Q5 (A = alkali metal; Q = chalcogen). γ-RbBi3S5 (I), α-RbBi3Se5 (II), β-RbBi3Se 5 (III), γ-RbBi3Se5 (IV), CsBi 3Se5 (V), RbBi3Se4Te (VI), and RbBi3Se3Te2 (VII) were synthesized from A 2Q (A = Rb, Cs; Q = S, Se) and Bi2Q3 (Q = S, Se or Te) at temperatures above 650 °C using appropriate reaction protocols. γ-RbBi3S5 and α-RbBi3Se 5 have three-dimensional tunnel structures while the rest of the compounds have lamellar structures. γ-RbBi3S5, γ-RbBi3S5, and its isostructural analogues RbBi 3Se4Te and RbBi3Se3Te2 crystallize in the orthorhombic space group Pnma with a = 11.744(2) Å, b = 4.0519(5) Å, c = 21.081(3) Å, R1 = 2.9%, wR2 = 6.3% for (I), a = 21.956(7) Å, b = 4.136(2) Å, c = 12.357(4), Å, R1 = 6.2%, wR2 = 13.5% for (IV), and a = 22.018(3), Å, b = 4.2217(6), Å, c = 12.614(2) Å, R1 = 6.2%, wR2 = 10.3% for (VI). γ-RbBi 3S5 has a three-dimensional tunnel structure that differs from the Se analogues, α-RbBi3Se5 crystallizes in the monoclinic space group C2/m with a = 36.779(4) Å, b = 4.1480(5), Å, c = 25.363(3), Å, β = 120.403(2)o, R1 = 4.9%, wR2 = 9.9%. β-RbBi3Se5 and isostructural CsBi3Se 5 adopt the space group P21/m with a = 13.537(2), Å, b = 4.1431(6), Å, c = 21.545(3) Å, β = 91.297(3)°, R1 = 4.9%, wR2 = 11.0% for (III) and a = 13.603(3), Å, b = 4.1502(8) Å, c = 21.639(4), Å, β = 91.435(3)°, R1 = 6.1%, wR2 = 13.4% for (V). α-RbBi3Se5 is also three-dimensional, whereas β-RbBi3Se5 and CsBi3Se5 have stepped layers with alkali metal ions found disordered in several trigonal prismatic sites between the layers. In γ-RbBi3Se5 and RbBi3Se4Te, the layers consist of Bi 2Te3-type fragments, which are connected in a stepwise manner. In the mixed Se/Te analogue, the Te occupies the chalcogen sites that are on the "surface" of the layers. All compounds are narrow band-gap semiconductors with optical band gaps ranging 0.4-1.0 eV. The thermal stability of all phases was studied, and it was determined that γ-RbBi 3Se5 is more stable than the and α- and β-forms. Electronic band calculations at the density functional theory (DFT) level performed on α-, β-, and γ-RbBi3Se 5 support the presence of indirect band gaps and were used to assess their relative thermodynamic stability.

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