Reversible topochemical polymerization and depolymerization of a crystalline 3D porous organic polymer with C-C bond linkages

Three-dimensionally connected porous organic polymers are of in-terest because of their potential in adsorption, separation, and sensing, among others. When crystalline, they also afford accurate structure description, which in turn can enable particular functions. However, crystallization of three-dimensional (3D) polymers is chal-lenging. This is especially true when targeting polymerization via stable C-C bonds, whose formation is usually irreversible and does not allow for error correction typically required for crystallization. Here, we report polyMTBA, the first 3D-connected crystalline organic polymer with permanent porosity, here formed via C-C link-ages. High crystallinity is achieved by solid-state topochemical reac-tion within monomer MTBA crystals. polyMTBA is recyclable via thermal depolymerization and is solution processable via its soluble monomers. These results reveal topochemical polymerization as a compelling methodology for generating stable, crystalline, and porous 3D organic frameworks.

Automated summary

In this study, the first 3D-connected crystalline organic polymer with permanent porosity, polyMTBA, was reported. Its formation mechanism and properties were described in detail, providing a new approach for topochemical polymerization.