Confined Polymerization in Highly Ordered Mesoporous Organosilicas

Hybrid mesoporous organosilica exhibiting crystal‐like order in the walls provided an ideal channel reaction vessel for the confined polymerization of acrylonitrile (PAN). The resulting high‐molecular‐mass PAN fills the channels at high yield and forms an ordered nanostructure of polymer nanobundles enclosed into the hybrid matrix. The in situ thermal transformation of PAN into rigid polyconjugated and, eventually, into condensed polyaromatic carbon nanofibers, retains the periodic architecture. Simultaneously, the matrix evolves showing the fusion of the p‐phenylene rings and the cleavage of carbon?silicon bonds: this gives rise to graphitic‐carbon/silica nanocomposites containing hyper‐oxydrylated silica nanophases. Interestingly, the 3D hexagonal mesostructure survives in the carbonaceous material. The exploitation of porous materials of high capacity and a hybrid nature, for polymerization in the confined state, followed by high temperature treatments, allowed us to achieve unique and precisely fabricated nanostructures, thus paving the way for the construction of fine‐tuned electronic and light‐harvesting materials.