Details

Autor(en) / Beteiligte

• Mayer, Kerstin
• Dums, Jasmin V
• Benda, Christian B
• Klein, Wilhelm
• Fässler, Thomas F

Titel

Solvate-Induced Semiconductor to Metal Transition: Flat 1 ∞ [Bi 1- ] Zigzag Chains in Metallic KBi⋅NH 3 versus 1 ∞ [Bi 1- ] Helices in Semiconducting KBi

Ist Teil von

• Angewandte Chemie (International ed.), 2020-04, Vol.59 (17), p.6800

Ort / Verlag

Germany

Erscheinungsjahr

2020

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Polymeric [Bi] in KBi⋅NH 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 [KBi] layers are separated by intercalated NH 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 [Bi ] isolated in K [K(18-crown-6)] [Bi ]⋅9 NH . Although [Bi ] should exhibit one localized double bond, electron delocalization is observed in analogy to the lighter homologues [P ] and [As ] . Both compounds were characterized by single-crystal X-ray structure determination.