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Solvate-Induced Semiconductor to Metal Transition: Flat 1 [Bi1- ] Zigzag Chains in Metallic KBi⋅NH3 versus 1 [Bi1- ] Helices in Semiconducting KBi.
Mayer, Kerstin; Dums, Jasmin V; Benda, Christian B; Klein, Wilhelm; Fässler, Thomas F.
Afiliação
  • Mayer K; Technische Universität München, Institute of Inorganic Chemistry, Lichtenbergstrasse 4, Garching bei München, 85747, Germany.
  • Dums JV; Technische Universität München, Institute of Inorganic Chemistry, Lichtenbergstrasse 4, Garching bei München, 85747, Germany.
  • Benda CB; Technische Universität München, Institute of Inorganic Chemistry, Lichtenbergstrasse 4, Garching bei München, 85747, Germany.
  • Klein W; Technische Universität München, Institute of Inorganic Chemistry, Lichtenbergstrasse 4, Garching bei München, 85747, Germany.
  • Fässler TF; Technische Universität München, Institute of Inorganic Chemistry, Lichtenbergstrasse 4, Garching bei München, 85747, Germany.
Angew Chem Int Ed Engl ; 59(17): 6800-6805, 2020 Apr 20.
Article em En | MEDLINE | ID: mdl-31917887
ABSTRACT
Polymeric 1 ∞ [Bi]- in KBi⋅NH3 has planar zigzag chains with two-connected Bi atoms and metallic properties, whereas KBi, which has helical chains of Bi atoms, is semiconducting. The isomerization of the Bi chain is induced by solvate molecules. In the novel layered solvate structure uncharged 2 ∞ [KBi] layers are separated by intercalated NH3 molecules. These layers are a structural excerpt of the iso(valence)electronic CaSi, whose metallic properties arise from the planarity of the zigzag chain of Si atoms. Computational studies support this view, they show an anisotropic metallic behavior along the Bi chain. Electron delocalization is also found in the new cyclic anion [Bi6 ]4- isolated in K2 [K(18-crown-6)]2 [Bi6 ]⋅9 NH3 . Although [Bi6 ]4- should exhibit one localized double bond, electron delocalization is observed in analogy to the lighter homologues [P6 ]4- and [As6 ]4- . Both compounds were characterized by single-crystal X-ray structure determination.
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Ano de publicação: 2020 Tipo de documento: Article País de afiliação: Alemanha

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Ano de publicação: 2020 Tipo de documento: Article País de afiliação: Alemanha
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