Homologous silver bismuth chalcogenide halides (N, x)P. III. The (4, x)P, (5, x)P, and (7, x)P structure families of modular compounds with tunable composition and structure

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

Abstract

The crystal structures of six members of the homologous series with general formula [BiQX]2[AgxBi1-xQ2-2xX 2x-1]N+1 (Q = S, Se; X = Cl, Br; 1/2 ≤ x ≤ 1) and N = 4, 5, or 7 were determined by single-crystal X-ray diffraction. The series are characterized by the parameters N and x and are denoted (N, x)P. Ag3Bi4S6Cl3 (x = 0.60) (I), Ag 3.5Bi3.5S5Br4 (x = 0.70) (II) and Ag3.65Bi3.35Se4.70Br4.30 (x = 0.73) (III) belong to (4, x)P series Ag5xBi7-5xQ 12-10xX10x-3 and adopt the AgBi6S9 structure type. The (5, x)P compound Ag3.66Bi 4.34S6.68Br3.32 (IV), which corresponds to x = 0.61 in Ag6xBi8-6xS14-12xBr12x-4, crystallizes isostructurally to AgBi3S5. The compounds Ag4.56Bi5.44Se8.88Br3.12 (x = 0.57) (V) and Ag5.14Bi4.86S7.76Br4.24 (x = 0.64) (VI), which are members of (7, x)P series Ag 8xBi10-8xQ18-16xBr16x-6, adopt the Ag3Bi7S12 structure type. In the monoclinic crystal structures (space group C2/m) two kinds of layered modules alternate along [001]. Modules of type A uniformly consist of paired rods of face-sharing monocapped trigonal prisms around Bi atoms with octahedra around mixed occupied metal positions (M = Ag/Bi) between them. Modules of type B are composed of [MZ6] octahedra, which are arranged in NaCl-type fragments of thickness N. All structures exhibit Ag/Bi disorder in octahedrally coordinated metal positions as well as Q/X mixed occupation of some anion positions. Corresponding to their black color, all compounds are narrow-gap semiconductors (Eg = 0.35 eV for (II)). General characteristics of the entire class of (N, x)P compounds are gathered in a catalogue.

Details

OriginalspracheEnglisch
Seiten (von - bis)482-490
Seitenumfang9
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang634
Ausgabenummer3
PublikationsstatusVeröffentlicht - März 2008
Peer-Review-StatusJa

Externe IDs

ORCID /0000-0002-2391-6025/work/159171918

Schlagworte

ASJC Scopus Sachgebiete

Schlagwörter

  • Bismuth, Chalcogenides, Halides, Pavonite, Silver, Solid solutions