The free radical  polymerization of alkene monomers is one of the main methods for preparing polymer compounds. Compared to ionic and coordination polymerizations, a significant challenge in free radical polymerization is stereochemical control: due to the planar configuration of the active centers, the polymerization process is poorly controllable, and it is not easy to obtain polymer products with high stereoregularity. At the same time, stereoregularity, as an important structural parameter of polymers, has a significant impact on the crystallinity, mechanical strength, glass transition temperature, and other properties of the polymers. To achieve stereoregular free radical polymerization, traditional methods often require the use of monomers with large steric hindrance, special solvents, or the addition of stoichiometric/adiametric Lewis acids, which still have room for improvement in terms of cost and applicability. Therefore, developing a general catalytic strategy to control the stereochemistry of free radical polymerization reactions is an important issue with both scientific and practical value.

To address this issue, we hope to utilize the principles of molecular recognition to design receptor molecules with appropriate size, steric hindrance, and electronegativity, which can specifically bind to the polymerization monomers or the ends of polymer chains through non-covalent interactions. By leveraging the steric hindrance and asymmetric chemical environment provided by the receptor molecules, we aim to continuously induce stereoselective free radical addition reactions, achieving controlled chain growth, and ultimately obtaining polymer products with high stereoregularity. Furthermore, by combining these supramolecular catalysts with living polymerization techniques, we aim to simultaneously control the molecular weight, end groups, and stereostructure of the polymers, serving the precise synthesis of high-performance polymer materials.