An Unprecedented 1∞ [Ge 9 ] 2− Polymer: A Link between Molecular Zintl Clusters and Solid‐State Phases

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.