Nanostructured Polysilanes

Polysilane-based nanostructured composites were synthesized by the inclusion of poly(di-w-hexylsilane) (Mw = 53,600) into mesoporous, Si-OH-rich silica with a pore size of 2.8 nm.81 Two PL bands are observed for the composite. A narrow band at 371 nm, assigned to a PDHS film on a quartz substrate is blue shifted by 20 nm, a shift attributed to the polymer being incorporated into the pores.82 The size of the monomeric unit of the PDHS is about 1.6 nm, so only one polymer chain can be incorporated into a mesopore with a diameter of 2.8 nm. The narrow PL band at 350 nm is due to the reduction of the intermolecular interactions between polymer chains. This narrow PL band at 350 nm is assigned to the excited state of the linear polymer chain.81 Also, a new broad band of visible fluorescence at 410 nm appeared, which is assigned to localized states induced by conformational changes of the polymer chains caused by its interaction with the silanol (Si-OH) covered pore surface. Visible luminescence in nanosize PDHS is observed only when the polymer was incorporated in hexagonal pores of 2.8 nm and is not seen for the polymer incorporated into cubic pores of 2.8 nm diameter or hexagonal pores of 5.8 nm diameter. 

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Ebihara, K., Koshihara, S., Yoshimoto, M., Maeda, T., Ohnishi, T., Koinuma, H., and Fujiki, M. Direct observation of helical polysilane nanostructures by atomic force microscopy, jpn.. Appl. Phys., 36, L1211 (1997). 

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