Reversible topochemical polymerization and depolymerization of a crystalline 3D porous organic polymer with C–C bond linkages
Reversible topochemical polymerization and depolymerization of a crystalline 3D porous organic polymer with C–C bond linkages
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DOI：
10.1016/j.chempr.2022.07.028
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发表时间：
2022-08
期刊：
影响因子：
23.5
通讯作者：
Chenyue Sun;Julius J. Oppenheim;Grigorii Skorupskii;Luming Yang;M. Dincǎ
中科院分区：
文献类型：
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作者：
Chenyue Sun;Julius J. Oppenheim;Grigorii Skorupskii;Luming Yang;M. Dincǎ
三维连接的多孔有机聚合物由于其在吸附、分离和传感等方面的潜力而受到关注。当结晶时，它们还提供准确的结构描述，这反过来可以实现特定的功能。然而，三维（3D）聚合物的结晶是具有挑战性的。当通过稳定的C-C键靶向聚合时尤其如此，其形成通常是不可逆的，并且不允许结晶通常所需的误差校正。在这里，我们报告polyMTBA，第一个3D连接的结晶有机聚合物与永久孔隙，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MTBA可通过热解聚回收，并可通过其可溶性单体进行溶液加工。这些结果揭示了拓扑化学聚合作为一种引人注目的方法，用于产生稳定的，结晶的，和多孔的3D有机框架。
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 reportpolyMTBA, 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 monomerMTBAcrystals.polyMTBAis 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.