Stable silanetriols that contain tert-alkoxy groups: versatile precursors of siloxane-based nanomaterials

Novel tert-alkoxysilanetriols (ROSi(OH)(3), R=adamantyl and 3-ethyl-3-pentyl) have been prepared from the corresponding tert-alkoxytrichlorosilanes and successfully used as molecular building blocks to produce ordered siloxane-based nanomaterials. Controlled hydrolysis of the alkoxytrichlorosilanes led to the formation of crystalline powders of alkoxysilanetriols that were stable under ambient conditions. Solid-state polycondensation of the alkoxysilanetriols occurred upon heating, which led to the formation of ordered silica-organic nanocomposites with laminated morphologies. On the other hand, silylation of the tert-alkoxysilanetriols with chlorotrimethoxysilane enabled us to synthesize well-defined oligomeric alkoxysilanes (ROSi[OSi(OMe)(3)](3)). Hydrolysis and polycondensation of these oligomers followed by acid treatment gave microporous silica with narrow pore size distributions. Thus, tert-alkoxy groups serve not only as protecting groups of siloxane species to regulate hydrolysis and polycondensation, but also as templates to generate micropores thereby providing unique synthetic pathways for the design of ordered silica-based materials.