Polysilanes photochemistry

Polysilanes as Photoinitiators. Since polysilanes photolyze to give silyl radicals,(21) as explained in the section on photochemistry above, they can be used as photoinitiators for radical processes such as polymerization.38 As can be seen from the information in Table II, this process is a fairly general one a variety of... 

Photochemistry and photophysics of polysilanes is also discussed in the Chapter by Zeigler, Harrah and Johnson in this volume, ref. 15. 

In summary, the production of substituted silylenes and silyl radicals upon exhaustive irradiation at 254 nm of polysilane high polymers suggested that the polymer photochemistry resembled that previously reported for short chain acyclic and cyclic oligomers (39). More recent experiments, however, have suggested that the photochemical mechanism for the degradation of the high polymers is more complex than first envisioned (vide infra) (48). 

MILLER ETAL. Polysilanes Solution Photochemistry Lithography... 

The ladder polysilanes also show interesting photochemistry on irradiation with a high-pressure mercury lamp, the tricyclic ladder extruded the transient intermediate four-membered cyclic disilene which could be trapped using methanol, 1,3-butadiene, and anthracene, as shown in Scheme 38. 

Polysilanes absorb electromagnetic energy and undergo chain scission. This is an extremely important property of these polymers in terms of applications, Photochemistry is exhibited both in solution and in the solid slate. 

Polysilane high polymers possessing fully saturated all-silicon backbone have attracted remarkable attention recently because of their unique optoelectronic properties and their importance in possible applications as photoresists, photoconductors, polymerization initiators, nonlinear optical materials etc. A number of review articles have been published on this topic4-9. The studies in this field have stimulated both experimental and theoretical chemists to elaborate on understanding the excited state nature of polysilanes and oligosilanes and of their mechanistic photochemistry. 

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