An Unprecedented1∞[Ge9]2− Polymer: A Link between Molecular Zintl Clusters and Solid-State Phases

Abstract

A chain of vertex-linked "bare" nido-Ge(9)(2-) clusters (shown in the picture) is featured by the novel polymeric Zintl anion formed from the binary alloy "KGe(4)", ethylenediamine, and [18]crown-6. The polymerization of nido-Ge(9)(4-) clusters is counterintuitive to known two-electron oxidation behavior of nido clusters and the existence of the isolated closo-Ge(9)(2-) ion. The novel semiconducting cluster "wire" establishes direct structural and mechanistic links between molecular Zintl cluster ions with the extended structures of Zintl phases and elemental nanophase materials.