Directional Building Blocks Determine Linear and Cyclic Silicon Architectures

Silicon nanomaterials
combine earth abundance and biodegradability
with exceptional electronic properties. Strategic synthesis promises
access to novel architectures with well-defined surface structure,
size, and shape. Herein, we describe a five-step synthesis of functional
macrocyclic polysilanes. Comparison of the materials isolated from
isomeric building blocks provides evidence that building block directionality
controls the shape of the resulting nanomaterial. Infrared (IR) and 1H and 29Si NMR spectroscopies, coupled to computational
data, provide evidence of a well-defined Si–H and Si–Me
terminated structure. The intrinsic porosity and the polarization
arising from the hydridic character of the Si–H bond suggest
applications in lithium-ion batteries, which are supported by quantum
chemical calculations.