SuFExable polymers with helical structures derived from thionyl tetrafluoride

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 SOF 4 -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. Sulfur( vi ) fluoride exchange (SuFEx)—a type of click chemistry that generates S VI -centred covalent linkages—has previously been used for polymer synthesis. Now, modular SuFEx polymerization using SOF 4 has been used to generate helical polymers. Unlike previous examples of SuFEx polymerization, the backbone retains S VI –F motifs and therefore is able to undergo further SuFEx click reactions, enabling facile and efficient post-polymerization modification.