SuFExable polymers with helical structures derived from thionyl tetrafluoride

Li, Suhua; Li, Gencheng; Gao, Bing; Pujari, Sidharam P.; Chen, Xiaoyan; Kim, Hyunseok; Zhou, Feng; Klivansky, Liana M.; Liu, Yi; Driss, Hafedh; Liang, Dong Dong; Lu, Jianmei; Wu, Peng; Zuilhof, Han; Moses, John; Sharpless, Barry


Sulfur(vi) fluoride exchange (SuFEx) is a category of click chemistry that enables covalent linking of modular units through sulfur(vi) connective hubs. The efficiency of SuFEx and the stability of the resulting bonds have led to polymer chemistry applications. Now, we report the SuFEx click chemistry synthesis of several structurally diverse SOF4-derived copolymers based on the polymerization of bis(iminosulfur oxydifluorides) and bis(aryl silyl ethers). This polymer class presents two key characteristics. First, the [–N=S(=O)F–O–] polymer backbone linkages are themselves SuFExable and undergo precise SuFEx-based post-modification with phenols or amines to yield branched functional polymers. Second, studies of individual polymer chains of several of these new materials indicate helical polymer structures. The robust nature of SuFEx click chemistry offers the potential for post-polymerization modification, enabling the synthesis of materials with control over composition and conformation. [Figure not available: see fulltext.]