Reversible Topochemical Polymerization and Depolymerization of a Crystalline Three-Dimensional Porous Organic Polymer with C–C Bond Linkages

12 October 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Three-dimensionally connected porous organic polymers are of interest 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 challenging. 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 linkages. High crystallinity is achieved by solid-state topochemical reaction 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.


Porous organic polymer
Crystalline polymer
Degradable polymer


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