This review systematically summarizes the development and application of various synthetic strategies for covalent crystals, including the modulator approach, seed-mediated growth, interfacial synthesis, and supercritical CO₂ synthesis. It maps out the developmental trajectory of the large-size single-crystal COF field from multiple dimensions, such as polymerization reaction type, assembly pathway, characteristic building blocks, and crystallization medium. The critical role of the modulator strategy in facilitating the discovery of new single-crystal COF structures and the elucidation of novel phenomena is particularly emphasized. Finally, future development trends in the field are prospected from four aspects: the iteration of assembly methods, multi-level structural analysis, understanding of complex assembly mechanisms, and exploration of unique applications. This review showcases the transformative progress of single-crystal COFs from“nonexistence to existence”and from“difficulty to ease”, offering a new paradigm for the integration of organic synthetic chemistry and crystal engineering, and paving a new path for the creation of novel artificial crystals.

原文链接：https://download.sciengine.com/cfs/files/pdfs/view/0023-074X/FEDF46E96A8C4820AFF99E09D9AFF7E3.pdf