Synthesis, Properties, and Derivatization of Poly(dihydrogermane): A Germanium-based Polyethylene Analogue

Polygermanes are germanium-based analogues of polyolefins and possess polymer backbones made up catenated Ge atoms. In the present contribution we report the preparation of a stable germanium polyethylene analogue – polydihydrogermane (i.e., (GeH2)n) – via two straightforward approaches that involve topotactic deintercalation of the CaGe Zintl phase. The resulting (GeH2)n possess morphologically dependent chemical and electronic properties and thermally decompose to yield amorphous hydrogenated Ge. We also show that the resulting (GeH2)n provide a platform from which functionalized polygermanes can be prepared via thermally-induced hydrogermylation-mediated pendant group substitution. This facile one-step derivatization reaction exploits Ge–H reactivity and opens the door to a wide array of tailored functional polygermanes.