Covalent Folding of Fluorinated Polyphenylene by Sulfur Fluorine Annulative Substitution

We report that fluorinated polyphenylene P50 undergoes folding-like sulfur fluorine annulative substitution (SFAS) to form a well-defined tubular helix H50. This is achieved with atomic precision in an exceptionally efficient manner, involving the simultaneous transformation of 98 C-F bonds with the yield per reaction site approaching 99.9%. The desired product H50 features a fully fused dibenzothiophene skeleton of 5.8 helical turns in total. It is truly monodisperse (Đ = 1.0) in nature, allowing for thorough spectroscopic characterizations. Unambiguous single crystal X-ray structure, distinct chiroptical properties, and intriguing through-cavity threading complexation are described. These results, in addition to those of H50's lower congeners, H34 and H18, illustrate the great potential of folding-like SFAS in shaping random-coiled polymer chains into higher-order functional structures.