Polysilanes and Related Polymers

In polysilane polymers, the polymer backbone is made up entirely of silicon atoms. Therefore these materials differ from other important inorganic polymers, the siloxanes and phosphazenes, in which the polymer chain is heteroatomic. Structurally, they are more closely related to homoatomic organic polymers such as the polyolefins. However, because the units in the main chain are all silicon atoms, the polysilanes exhibit quite unusual properties. The cumulated silicon-silicon bonds in the polymer chain allow extensive electron delocalization to take place, and this delocalization of the sigma electrons in the Si-Si bonds gives the polysilanes unique optical and electronic properties. Many of the potential technical uses, as well as the remarkable properties, of polysilanes result from this unusual mobility of the sigma electrons. 

The polysilanes can be regarded as one-dimensional analogs to elemental silicon, on which, of course, nearly all of modem electronics is based. The photophysical behavior of polysilanes is not approached by any other materials, save for the less stable and more costly polygermanes and polystannanes. The remarkable properties of polysilanes have led to intense interest, and to numerous proposed high-tech applications. But the great promise of polysilanes as materials has yet to be realized. Their only commercial use at present is as precursors to silicon carbide ceramics, an application which takes no advantage of their optical or electronic properties. 

Linear polysilane polymers, properly called poly(silylene)s, can be obtained as homopolymers or copolymers. Continuation of the polysilane chain consumes two of the four valences of each silicon atom the other two are taken up by pendent groups, which may be the same (5.1) or different (5.2). Copolymers (5.3), which contain two or more kinds of silicon atoms, can be made up from units like those in 5.1 or 5.2. A typical example is the copolymer of Me2Si and PhMeSi units, 

The properties of the polysilanes, like those of the polyphosphazenes, depend greatly on the nature of the substituent groups. Polysilanes cover the entire range of properties from highly crystalline and insoluble, through partially crystalline, flexible solids, to glassy amorphous materials and rubbery elastomers. 

Until recently, it was thought that polysilanes would be either intractable or unstable. In his famous book, Eugene G. Rochow, the father of the silicone industry, dismissed poly silane polymers in this way  

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