Fabrication of Double-Stranded Vinyl Polymers Mediated by Coordination Nanochannels

Although double-stranded structures are commonly found in biopolymers, a general and versatile methodology for fabricating double-stranded synthetic polymers has not yet been developed. Here, we report a new approach for synthesizing double-stranded polymers composed of polystyrene and poly(methyl methacrylate). We conducted crosslinking radical polymerization inside a metal-organic framework (MOF), which had one-dimensional channels with diameters similar to the thickness of two polymer chains. Effective spatial constraint within the MOF pores facilitated highly regulated crosslinking reactions between two polymer chains with extended conformations. Remarkably, the obtained double-stranded polymers were soluble in many organic solvents, even at a high crosslinking ratio (20%), unlike conventional crosslinked polymers. Notably, this stable duplex topology, which was inaccessible using previous methods, endowed the double-stranded vinyl polymers with unusual properties in the solution and bulk states. By designing the properties of the MOF nanochannels, the proposed technique can contribute to the development of a wide range of synthetic polymer duplexes.