Exploring high-connectivity three-dimensional covalent organic frameworks: topologies, structures, and emerging applications.

Covalent organic frameworks (COFs) represent a highly versatile class of crystalline porous materials, formed by the deliberate assembly of organic building units into ordered two-dimensional (2D) and three-dimensional (3D) structures. Their unique combination of topological precision and tunable micro- or mesoporous architectures offers unmatched flexibility in material design. By selecting specific building units, reactive sites, and functional groups, COFs can be engineered to achieve customized skeletal, porous, and interfacial properties, opening the door to materials with optimized performance for diverse applications. Among recent advances, high-connectivity 3D COFs have emerged as a particularly exciting development, with their intricate network structures enabling unprecedented levels of structural complexity, stability, and functionality. This review provides a comprehensive overview of the synthesis strategies, topological design principles, structural characterization techniques, and emerging applications of high-connectivity 3D COFs. We explore their potential across a broad range of cutting-edge applications, including gas adsorption and separation, macromolecule adsorption, dye removal, photocatalysis, electrocatalysis, lithium-sulfur batteries, and charge transport. By examining these key areas, we aim to deepen the understanding of the intricate relationship between structure and function, guiding the rational design of next-generation COF materials. The continued advancements in this field hold immense promise for revolutionizing sectors such as energy storage, catalysis, and molecular separation, making high-connectivity 3D COFs a cornerstone for future technological innovations.