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.

三维连接的多孔有机聚合物因其在吸附、分离和传感等方面的潜力而备受关注。当结晶时，它们还提供准确的结构描述，这反过来又可以实现特定的功能。然而，三维 (3D) 聚合物的结晶具有挑战性。当通过稳定的 C-C 键进行聚合时尤其如此，其形成通常是不可逆的，并且不允许进行结晶通常所需的纠错。在这里，我们报告了polyMTBA，这是第一种具有永久孔隙率的 3D 连接结晶有机聚合物，这里通过 C-C 键形成。高结晶度是通过单体MTBA晶体内的固态拓扑化学反应实现的。聚甲基丙烯酸甲酯可通过热解聚回收，并可通过其可溶性单体进行溶液加工。这些结果表明，拓扑化学聚合是生成稳定、结晶和多孔 3D 有机框架的一种引人注目的方法。