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 germanium polyethylene analogue, polydihydrogermane (GeH2)n, via two straightforward approaches that involve topotactic deintercalation of Ca ions from the CaGe Zintl phase. The resulting (GeH2)n possesses morphologically dependent chemical and electronic properties and thermally decomposes to yield amorphous hydrogenated Ge. We also show that the resulting (GeH2)n provides a platform from which functionalized polygermanes can be prepared via thermally induced hydrogermylation-mediated pendant group substitution.