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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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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