There is a constant demand for materials with new or improved properties. Ideal syntheses of new materials will allow rapid preparation of libraries of materials whose properties can be tuned to match those required for a given application. Here we present three such syntheses. A "Click" based approach to new N-vinyl monomers provides a family of monomers with various properties reminiscent of vinylpyridines (polarity, ion and hydrogen bonding), styrene (thermal stability, aromatic core), acrylates (modularity, functionality), and reactivity similar to other N-vinyl monomers such as vinylimidazole. The polymerization of these monomers can be controlled my RAFT/MADIX or NMP to give random or block copolymers with properties distinct from the isomeric poly(C-vinyl triazoles).

Another highly efficient reaction, the dimerization of ketenes, is used to prepare a series of rigid cyclobutanediol monomers. The multifaceted reactivity of Meldrum's acid is used to access a structurally diverse range of ketenes and resulting monomers. New polyesters based on these monomers provide improved stability over the structurally similar commercial monomer tetramethylcyclobutanediol. These new monomers should allow preparation of copolyesters capable of replacing bisphenol A-based polycarbonate in a number of applications, specifically related to the food industry, as the BPA monomer has been demonstrated to be a health hazard.

Finally, an improved synthetic route to the conjugated building block dithienothiophene is described. This electron rich moiety can be copolymerized with a series of less electron rich monomers to provide conjugated polymers with distinct and unique optoelectronic properties. We demonstrate the importance of introducing a pi-conjugated linker to alleviate steric issues which can kink the polymer backbone and disrupt conjugation.