Optically active polysilylenes: State-of-the-art chiroptical polymers

Controlled synthesis, chiroptical characterization and manipulation of arti ficial helical polymers are challenging issues in modern polymer stereochem istry. Although many artificial polymers adopting a preferential screw-sens e helical structure have been investigated optically active polysilylenes b earing chiral side chains may be among the most suitable to elucidate the i nherent nature of the helical structure, since these polymers offer powerfu l spectroscopic probes as a result of their ideal chromophoric and fluoroph oric main chain properties around 300-330 nm. The present paper will review comprehensively the helix-property-functionality relationship between side chain structure, global and local main chain conformation, (chir)optical p roperties, electronic properties, several helical cooperative phenomena, th e effects of temperature and solvent polarity, and molecular imaging. This knowledge and understanding of the nature of the polysilylene helix might c onstitute a bridge between artificial polymers and biopolymers and will ass ist in designing and controlling new types of helical polymers directed to diverse screw-sense-related properties and applications in the future.