Li Xilin, Zhao Tongyi, Wang Fengzhen, Wu Wenxuan, Sun Yali, Ren Hao, Sun Fuxing
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University Changchun China
Chem Sci. 2025 Mar 25;16(17):7339-7346. doi: 10.1039/d5sc01227a. eCollection 2025 Apr 30.
Three-dimensional (3D) covalent organic frameworks (COFs) offer tremendous potential for a range of applications due to their unique structural and porous features. However, achieving the reticular synthesis of 3D COFs with regulated pores through isoreticular expansion remains a significant challenge, primarily due to the occurrence of interpenetration. In this study, we present a novel strategy that utilizes high-coordinated building blocks, acting as a binodal group of tetrahedral nodes, to synthesize isoreticular 3D COFs (JUC-300 to -302) with tunable pore sizes and uncommon non-interpenetrated -derived topology. The pore sizes of these COFs were successfully tuned from 1.6 to 5.2 nm. The mesopores with a size of 5.2 nm in JUC-302 are the largest reported among 3D COFs to date and demonstrated the effective incorporation of a large protein, myoglobin. The strategy provides a new pathway for synthesizing isoreticular 3D COFs with reduced interpenetration, enabling applications that depend on various pore sizes.
三维(3D)共价有机框架(COFs)由于其独特的结构和多孔特性,在一系列应用中具有巨大潜力。然而,通过等规膨胀实现具有规整孔道的3D COFs的网状合成仍然是一项重大挑战,主要原因是会出现互穿现象。在本研究中,我们提出了一种新颖的策略,利用高配位构筑单元作为四面体节点的双节点基团,来合成具有可调孔径和罕见非互穿衍生拓扑结构的等规3D COFs(JUC - 300至 - 302)。这些COFs的孔径成功地从1.6纳米调节到5.2纳米。JUC - 302中尺寸为5.2纳米的中孔是迄今为止3D COFs中报道的最大中孔,并证明了能够有效包合一种大蛋白——肌红蛋白。该策略为合成互穿减少的等规3D COFs提供了一条新途径,从而实现了依赖于各种孔径的应用。