Silyl Radicals in Polymers and Materials

The formation of silyl radicals in the exhaustive photolysis of the silane polymers was indicated by the isolation of disilanes of general structure (HSiRR SiRR H) as shown in Table 1. These materials accumulate in the photolysate and are photostable as they absorb only weakly at the irradiation wavelength (254 nm). Longer chain silanes are presumably continuously degraded under the conditions of the exhaustive irradiation. 

The chemistry of silyl radicals in the last decade has expanded considerably. Silyl radicals play an important role in diverse areas such as organic synthesis, material science and polymer chemistry. Since the early works have already been reviewed by one of the authors1, the purpose of this chapter is to bring together all the recent developments. Furthermore,... 

Polysilane derivatives constitute a new class of radiation-sensitive materials with interesting physical and electronic properties. The photochemical decomposition of polymers containing disilanyl units seems adequately explained by silicon-silicon bond homolysis and subsequent radical reactions. The solution photochemistry of longer silicon catenates results in the extrusion of substituted monomeric silylenes, as well as the formation of silyl radicals produced by chain homolysis. Recent studies indicating that the... 

---