A Non-Hydrolytic Sol-Gel Route to Organic-Inorganic Hybrid Polymers: Linearly Expanded Silica and Silsesquioxanes.

Condensation reactions of chlorosilanes (SiCl and CHSiCl) and bis(trimethylsilyl)ethers of rigid, quasi-linear diols (CH)SiO--OSi(CH) ( = 4,4'-biphenylene () and 2,6-naphthylene ()), with release of (CH)SiCl as a volatile byproduct, afforded novel hybrid materials that feature Si-O-C bridges. The precursors and were characterized using FTIR and multinuclear (H, C, Si) NMR spectroscopy as well as single-crystal X-ray diffraction analysis in case of . Pyridine-catalyzed and non-catalyzed transformations were performed in THF at room temperature and at 60 °C.