Help Privacy Policy Disclaimer
  Advanced SearchBrowse




Journal Article

Pentagonal Bismuth Antiprisms with Endohedral Palladium or Platinum Atoms by Low-Temperature Syntheses


Ruck,  Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available

Groh, M. F., Wolff, A., Wahl, B., Rasche, B., Gebauer, P., & Ruck, M. (2017). Pentagonal Bismuth Antiprisms with Endohedral Palladium or Platinum Atoms by Low-Temperature Syntheses. Zeitschrift für anorganische und allgemeine Chemie, 643, 69-80. doi:10.1002/zaac.201600354.

Cite as: https://hdl.handle.net/11858/00-001M-0000-002D-09FC-9
We present the syntheses, crystal structures, and properties of five metal-rich salts containing the Bi-10(4+) pentagonal antiprism with an endohedral palladium or, for the first time, platinum atom. Tetragonal [Pt@Bi-10](AlBr4)(4) [P4(2)/n at 296(1) K; Pstyled-content style "text-decoration:overline"4/styled-content at 150(2) K] was obtained by reacting platinum, bismuth, and bismuth tribromide in [BMIm]Br4.1AlBr(3) at 140 degrees C (BMIm = 1-butyl-3-methylimidazolium). Monoclinic [Pt@Bi-10](AlBr4)(2)(Al2Br7)(2) [P2(1)/n] occurs as by-product. The two corresponding palladium compounds result from the dissolution of Bi16PdCl22 in [BMIm]Br4.1AlBr(3). [Pd@Bi-10](AlBr4)(4) [P4(2)/n] adopts a disordered structure homeotypic to its platinum analog. [Pd@Bi-10](AlBr4)(2)(Al2Br7)(2) [P2(1)/n] is isostructural to [Pt@Bi-10](AlBr4)(2)(Al2Br7)(2). In all structures, the [M@Bi-10](4+) cations are well separated by the bromido-aluminate anions with inter-cluster BiBi distances longer than 520 pm. This is not the case in [Pd@Bi-10][Bi2Sn6Cl22], which crystallized from a tin-containing melt of the metals and BiCl3. In its monoclinic structure [P2(1)/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.