Nanostructured Silicas, a Platform for the Observation of Transient Radicals: Application to Sulfinyl Radicals

Diazenes, precursors of sulfinyl radicals, were used to functionalize nanostructured SBA-15 silicas either in the framework or on the pore by formation of covalent links, or by simple adsorption on the surface. Depending on their design and on the experimental conditions, these materials proved to be effective tools to study the behavior and the reactivity of arylsulfinyl radicals made persistent because of confinement effects. When the covalently linked precursors were irradiated at room temperature, a spectacular increase of the lifetime of the expected sulfinyl radicals was registered (up to 17 h). At higher temperature, upon thermal initiation at 473 K, the decomposition of the adsorbed precursor enabled visualization of the rearrangement of the corresponding arylsulfinyl radicals into sulfonyl radicals via O–S coupling.