1. Access to metastable [GeH2]n materials via a molecular "bottom-up" approach.
- Author
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Sinclair, Jocelyn, Medroa del Pino, William, Aku-Dominguez, Kwami, Minami, Yohei, Kiran, Anagha, Ferguson, Michael J., Yasuda, Makoto, and Rivard, Eric
- Subjects
BAND gaps ,THIN films ,METATHESIS reactions ,HYDRIDES ,BORYLATION ,OLIGOMERS - Abstract
We describe the application of a mild, molecular-based, hydride metathesis protocol for the preparation of metastable germanium(II) dihydrides with compositions approaching [GeH
2 ]n . The common starting material for this work [Ge(Ot Bu)2 ] was prepared in a high yield and shown to undergo Ot Bu/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(Ot Bu)2 ] with excess H3 B·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 Ot Bu/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(Ot Bu)2 ] is a suitable pre-catalyst for the borylation of aldehydes. [ABSTRACT FROM AUTHOR]- Published
- 2021
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