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The Subbromide Bi5Br4 – On the Existence of a Hidden Phase

  • Black and irregularly shaped crystals of the bismuth‐rich bromide Bi5Br4 were obtained as a by‐product of the reaction of CsBr, Bi, and BiBr3. X‐ray diffraction on a single‐crystal revealed its orthorhombic structure with the space group Pmmn (no. 59) and lattice parameters a = 1800.0(2) pm, b = 1476.1(1) pm, and c = 924.5(2) pm at 296 K. The structure is composed of Bi82+ and Bi95+ polycations and bromidobismuthate(III) anions according to the structured formula Bi5Br4 = Bi20Br16 = Bi82+Bi95+[BiBr5]2–[Bi2Br11]5–. Bi5Br4 is the bismuth‐richest among the bismuth subhalides containing isolated polycations. Extensive differential scanning calorimetry studies indicate that Bi5Br4 decomposes at 262 °C, i.e. one degree below the bismuth‐rich eutectic at 263 °C. All attempts towards a rational synthesis yielded predominantly the neighboring phases BiBr and Bi6Br7.

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Author: Falk Pabst, Jen‐Hui Chang, Kati FinzelORCiD, Miroslav KohoutORCiD, Peer SchmidtORCiD, Michael RuckORCiD
URL:https://onlinelibrary.wiley.com/doi/10.1002/zaac.201800149
DOI:https://doi.org/10.1002/zaac.201800149
Title of the source (English):Zeitschrift für Anorganische und Allgemeine Chemie
Document Type:Scientific journal article peer-reviewed
Language:English
Year of publication:2020
Tag:Bismuth; Bromine; Cluster; Crystal structure; Phase Diagrams; Polycations
Volume/Year:646
Issue number:3
First Page:149
Last Page:155
Faculty/Chair:Fakultät 2 Umwelt und Naturwissenschaften / FG Anorganische Chemie
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