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One-dimensional. sigma. -conjugated polysilylenes, science and technology

Zeigler, J.M.

This paper will focus on the electronic and photochemical properties of polysilylenes, with particular emphasis on the many resemblances in the electronic properties of polysilylenes to those of the familiar {pi}-conjugated polymers. In this context, the term {sigma}-conjugation'' will appear in this paper, as it is almost universally prevalent in the field. However, the use of this term should only be interpreted to suggest a correspondence in the electronic properties with those of {pi}-conjugated materials. No direct correspondence in electronic interactions at the atomic level is implied. In fact, the theoretical underpinnings of the mechanism of electron delocalization in {sigma}-bonded systems remain incomplete, at best. The systematic name polysilylene'' will be used in place of the equivalent and widely used term polysilane.'' In this context, these terms are intended to refer to polydiorganosilylenes, i.e. silicon backbones having substituents other than hydrogen. Moreover, since, with the exception of the commercial use of the intractable polydimethylsilylene as a precursor to {beta}-Sic fibers, the overwhelming majority of the interest in the field is in soluble polysilylenes, the discussion here will be of that greatly predominant group of the materials which are fully tractable and processible. 75 refs., 4 figs., 2 tabs.