Chapter 6 – Polysilanes

This chapter starts with an introduction to the field of polysilanes, covering briefly the key electronic and conformational aspects of σ-electron delocalization, its perturbation by substituents, and the resulting optoelectronic effects (particularly in the UV). The chapter then reviews the different polysilane synthetic approaches (Wurtz, dehydrocoupling, masked disilene, ring-opening, electroreductive, and redistribution), aiming to give the reader an understanding of the development, requirements, mechanism, applicability, modifications, and recent advances in each approach. Postpolymerization functionalization is then covered, discussing general approaches and giving recent examples. The chapter concludes with a section on applications.