‘Polysilanes’ is an important class of inorganic polymers having Si-Si σ-conjugation along the backbone. They exhibit extraordinary electronic and photophysical properties and find suitable optoelectronics applications. They are typically synthesized by Wurtz coupling reaction of dichlorodialkylsilane or dichlorodiphenylsilane or dichloroalkylphenylsilane and their combinations under drastic reaction conditions by using sodium dispersion in boiling toluene. In such a drastic condition, no functional groups sustain with polysilane polymer. In order to achieve such functional materials, researchers have been interested in synthesizing functional polysilane with a different functional group like a chiral group, azobenzene containing chromophore and other heteroatoms in their main chain or side chain. Therefore, it is a very challenging task to synthesize polysilanes having effective functionality integrated with their structures. However, the modern technological demand of materials leads to efforts to obtain polymers having functional and multifunctional activity in a single material. In this review article, we cover the synthesis of polysilane with functional activity via pre-polymerization and post-polymerization with a functional group.

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Polysilanes upon UV irradiation give rise to silyl macroradicals which are capable to initiate radical polymerization. Hence, chiral block functional polysilanes were synthesized by UV irradiation of poly(methylphenylsilane) (PMPS) with a vinyl chiral monomer, (R)‐N‐(1‐phenylethyl)methacrylamide (R‐NPEMAM). The synthesized copolymer samples were characterized by FTIR, NMR, and UV–vis spectroscopy. The number and weight average molecular weights of PMPS and synthesized chiral‐block‐PMPS were measured by GPC analysis. Two glass transition temperatures (Tg) of the synthesized materials clearly indicate the formation of chiral‐block‐PMPS copolymers. SEM analysis also indicated the synthesized organic–inorganic block copolymers. The optical and chiroptical properties of the synthesized materials were studied. The cotton effect is observed not only at 276 nm due to aromatic ring of the chiral monomer units but also at 325 nm which is associated with the Si–Si conjugation of PMPS block of synthesized functional polysilanes. Such tunable chirality may find potential application in optoelectronics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3626–3634

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