Lai Jiawei, Liu Shikai, Ma Wenjie, Wu Fei, Yu Ping, Mao Lanqun
College of Chemistry, Beijing Normal University, Beijing, China.
Beijing National Laboratory for Molecular Science, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing, China.
Nat Commun. 2025 Jul 2;16(1):6071. doi: 10.1038/s41467-025-61373-1.
Constructing three-dimensional covalent organic frameworks (3D COFs) remains a significant challenge compared to other areas of reticular chemistry. Most existing methods for constructing 3D COFs emphasize the necessity of at least one precursor being extended into 3D space. As a result, designing and synthesizing precursors with specific stereoconformations has become a dominant strategy for discovering new 3D COFs. In this study, we leverage the principle that the steric hindrance of intermediates during COF formation is inherently greater than that of the precursors. We demonstrate a strategy utilizing multinode porphyrin blocks with eight rotatable knots to create intermediates with steric hindrance-confined rigid stereoconformations, which can be viewed as active precursors for guiding 3D formation of COFs with high crystallinity. This approach paves an avenue to self-adaptive COF growth towards diverse 3D topologies that may circumvent obstacles for traditional precursor synthesis.
与网状化学的其他领域相比，构建三维共价有机框架（3D COF）仍然是一项重大挑战。大多数现有的构建3D COF的方法强调至少有一种前驱体扩展到三维空间的必要性。因此，设计和合成具有特定立体构象的前驱体已成为发现新型3D COF的主导策略。在本研究中，我们利用了COF形成过程中中间体的空间位阻本质上大于前驱体这一原理。我们展示了一种利用具有八个可旋转节点的多节点卟啉块来创建具有空间位阻受限刚性立体构象的中间体的策略，这些中间体可被视为用于引导具有高结晶度的COF三维形成的活性前驱体。这种方法为自适应COF向多种三维拓扑结构生长铺平了道路，这可能会规避传统前驱体合成的障碍。
