Xu Xiaoyi, Huang Ning
State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Polymer Science and Engineering, Zhejiang University Hangzhou 310058 China
Chem Sci. 2025 Sep 4. doi: 10.1039/d5sc05394c.
Covalent organic frameworks (COFs) are crystalline porous polymers with modular architectures and long-range order, offering exceptional tunability in pore structure and functionality. While conventional COFs are typically constructed from one or two types of monomers, recent advances have led to the emergence of multicomponent COFs (MC-COFs), which integrate three or more distinct building blocks within a single lattice. This strategy enables the precise spatial arrangement of diverse geometries, connectivity, and functionalities, imparting synergistic complexity beyond the reach of single- or binary-component systems. In this perspective, we present a comprehensive overview of MC-COF chemistry, organised around five representative construction strategies: isostructural and heterostructural copolymerization, multicomponent topological design, multicomponent reactions, and pore partitioning strategies. We further highlight how these frameworks enable emergent functions in catalysis, alkane isomer separation, chemical sensing, and radiotherapy through rational control of both periodic backbone structure and local chemical environments. Despite these advances, challenges persist in structural characterization, expanding the scope of dynamic linkages, and achieving predictive design of emergent properties. Looking forward, the integration of dynamic covalent chemistry, topological programming, and machine learning-driven design is expected to unlock the full potential of MC-COFs as next-generation multifunctional materials.
共价有机框架(COFs)是具有模块化结构和长程有序性的结晶多孔聚合物,在孔结构和功能方面具有出色的可调性。虽然传统的COFs通常由一两种单体构建而成,但最近的进展导致了多组分COFs(MC-COFs)的出现,即在单个晶格中整合了三种或更多不同的结构单元。这种策略能够实现不同几何形状、连接性和功能的精确空间排列,赋予单组分或双组分系统所无法企及的协同复杂性。从这个角度出发,我们围绕五种代表性的构建策略,即同构和异质结构共聚、多组分拓扑设计、多组分反应以及孔分隔策略,对MC-COF化学进行了全面概述。我们还进一步强调了这些框架如何通过对周期性主链结构和局部化学环境的合理控制,在催化、烷烃异构体分离、化学传感和放射治疗中实现新功能。尽管取得了这些进展,但在结构表征、扩展动态连接的范围以及实现新特性的预测设计方面仍存在挑战。展望未来,动态共价化学、拓扑编程和机器学习驱动设计的整合有望释放MC-COFs作为下一代多功能材料的全部潜力。