Convenient synthesis of fluorinated molecular nanoparticles constitutes a major challenge in the preparation of fluoro shape amphiphiles. To facilitate a modular and efficient synthesis, a “clickable” fluorinated polyhedral oligomeric silsesquioxane functionalized with seven 1H,1H,2H,2H-heptadecafluorodecyl side chains and one alkyne group on its periphery (FPOSS-alkyne) was designed and synthesized. It was then used to prepare a series of FPOSS-containing polymers with various architectures via “click” chemistry. FPOSS was tethered onto either homo-polystyrene (PS) or polystyrene-block-poly(ethylene oxide) (PS-b-PEO) at precise locations, including the chain end (FPOSS-PS, FPOSS-PS-b-PEO) or junction point [PS-(FPOSS)-PEO], or distributed randomly along a PS chain (PS/FPOSS). This study demonstrates the chemical robustness of the novel building block and establishes a general and efficient approach to introduce fluorous molecular clusters onto polymers, especially for high molecular weight polymers or those polymers with high fluoro contents. These precisely defined FPOSS-containing polymers could serve as model compounds to study the self-assembly behaviors of these shape amphiphiles in the bulk, solution and thin film.
