RESUMEN
A series of air-stable poly(cyclogermapentene)s were prepared via the dehydrocoupling of 1,1-dihydrocyclogermapentene monomers. Exposure of the resulting polygermanes to UV light led to elimination of organobutadiene from the polymer side chains and deposition of germanium metal. Overall, this study introduces a mild way to obtain patterns of semiconducting Ge for optoelectronic applications.
RESUMEN
We describe the application of a mild, molecular-based, hydride metathesis protocol for the preparation of metastable germanium(II) dihydrides with compositions approaching [GeH2]n. The common starting material for this work [Ge(OtBu)2] was prepared in a high yield and shown to undergo OtBu/H exchange at Ge with the hydride sources pinacolborane (HBpin), catecholborane (HBcat), and diisobutylaluminum hydride (DIBAL-H) to give the [GeH2]n materials as yellow to orange solids. Heating one of these [GeH2]n materials to 200 °C affords a narrowing of the optical band gap (from 2.5 eV) and the generation of amorphous Ge. Reaction of [Ge(OtBu)2] with excess H3B·SMe2 in toluene at 70 °C provides a convenient route to thin films of amorphous Ge, including its deposition onto soft substrates, such as polyethyleneterephthalate (PET). Accompanying computations give insight into the energetics of OtBu/H exchange at Ge, and reveal a general thermodynamic preference for branched structures of [GeH2]n oligomers over linear forms as the Ge chain becomes longer. We also show that [Ge(OtBu)2] is a suitable pre-catalyst for the borylation of aldehydes.