Ni, B.; Dong, X.;* Li, Y.; Chen, Z.; Lin, Z.; Huang, M.; Fu, Q.; Cheng, S. Z. D.;* Zhang, W.-B.* “Clicking” Fluorinated Polyhedral Oligomeric Silsesquioxane onto Polymers: A Modular Approach toward Shape Amphiphiles with Fluorous Molecular Clusters. Polym. Chem. 2014, 5, 3588-3597. [Link] [PDF]
 

Abstract
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.