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- Title
Pentagonal Bismuth Antiprisms with Endohedral Palladium or Platinum Atoms by Low-Temperature Syntheses.
- Authors
Groh, Matthias F.; Wolff, Alexander; Wahl, Bernhard; Rasche, Bertold; Gebauer, Paul; Ruck, Michael
- Abstract
We present the syntheses, crystal structures, and properties of five metal-rich salts containing the Bi104+ pentagonal antiprism with an endohedral palladium or, for the first time, platinum atom. Tetragonal [Pt@Bi10](AlBr4)4 [ P42/ n at 296(1) K; P 4 at 150(2) K] was obtained by reacting platinum, bismuth, and bismuth tribromide in [BMIm]Br·4.1AlBr3 at 140 °C (BMIm = 1-butyl-3-methylimidazolium). Monoclinic [Pt@Bi10](AlBr4)2(Al2Br7)2 [ P21/ n] occurs as by-product. The two corresponding palladium compounds result from the dissolution of Bi16PdCl22 in [BMIm]Br ·4.1AlBr3. [Pd@Bi10](AlBr4)4 [ P42/ n] adopts a disordered structure homeotypic to its platinum analog. [Pd@Bi10](AlBr4)2(Al2Br7)2 [ P21/ n] is isostructural to [Pt@Bi10](AlBr4)2(Al2Br7)2. In all structures, the [ M@Bi10]4+ cations are well separated by the bromido-aluminate anions with inter-cluster Bi ···Bi distances longer than 520 pm. This is not the case in [Pd@Bi10][Bi2Sn6Cl22], which crystallized from a tin-containing melt of the metals and BiCl3. In its monoclinic structure [ P21/ c], the cluster cations are arranged in chains along [001] with an inter-cluster distance of only 357 pm. Despite further structural evidence, DFT-based quantum chemical analysis gave no hint on inter-cluster bonding. According to the calculated band structure as well as resistivity and magnetic susceptibility measurements, the black compound is a diamagnetic semiconductor.
- Subjects
BISMUTH; PALLADIUM; LOW temperatures; INORGANIC synthesis; CRYSTAL structure
- Publication
Zeitschrift für Anorganische und Allgemeine Chemie, 2017, Vol 643, Issue 1, p69
- ISSN
0044-2313
- Publication type
Article
- DOI
10.1002/zaac.201600354