2026-10-14T13:37:36Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34025297 2026-09-29T17:06:36Z category_1 category_4 category_915 category_7 category_8 category_14 category_734 category_931 category_61 category_132 portal_63 item_type_2 month_year_09_2026

Tracing Covalent Organic Framework Assembly through Kinetic Deceleration Haoyuan Zhang (14501708) Chunqing Ji (9423565) Hao Yang (328526) Wei Zhao (14321) He Li (176971) Hong Ling Keok (25138064) Dan Zhao (285025) Biophysics Biochemistry Physical Sciences not elsewhere classified Medicine Microbiology Molecular Biology Biological Sciences not elsewhere classified Information Systems not elsewhere classified Developmental Biology Infectious Diseases synthesized without catalysts sustainable synthetic route structurally related systems structurally characterized millimeter sized single crystals guiding framework evolution gaining mechanistic insights direct experimental evidence covalent organic frameworks cof assembly pathway intermediate supramolecular assembly cof growth mechanisms quality crystalline cofs key intermediate formation mechanisms crystalline cofs systematic studies successfully captured scalable synthesis scalable routes reaction kinetics rational design rarely substantiated monomers plays kinetic deceleration isa ), intrinsic reactivity intentionally slowing free conditions enabling greener decisive role base condensation The formation mechanisms of covalent organic frameworks (COFs) have long been hypothesized but rarely substantiated by direct experimental evidence. Gaining mechanistic insights into this process is essential for the rational design and scalable synthesis of COFs. In this study, we employed the Schiff-base condensation, known for its high reactivity, to construct a series of β-ketoenamine COFs under mild, acid-free conditions. By intentionally slowing down the reaction kinetics, we successfully captured and structurally characterized millimeter-sized single crystals of an intermediate supramolecular assembly (ISA), which serves as a key intermediate in the COF assembly pathway. Systematic studies of structurally related systems further reveal that the intrinsic reactivity of the monomers plays a decisive role in guiding framework evolution. Notably, crystalline COFs can be synthesized without catalysts or modulators, establishing a green, sustainable synthetic route. Overall, this work provides fundamental insights into COF growth mechanisms, enabling greener, scalable routes to high-quality crystalline COFs. 2026-09-29T00:00:00Z Dataset Media 10.1021/jacs.6c13291.s002 https://figshare.com/articles/media/Tracing_Covalent_Organic_Framework_Assembly_through_Kinetic_Deceleration/34025297 CC BY-NC 4.0