Efficient and Atom-Economic Construction of Functional β-Ketoenamine-Linked Covalent Organic Frameworks via Amino-yne Click Polymerization

Covalent organic frameworks (COFs) are distinguished by their crystalline structures, permanent porosity, and versatile application potentials. However, the preparation of COFs typically requires prolonged reaction times, relies on specialized reaction conditions, or generates byproducts. Thus, to further promote the development of COFs, their synthesis through an efficient and atom-economic polymerization is highly desirable. In this work, thanks to its high efficiency and dynamic nature of its products, the metal-free and atom-economic amino-yne click polymerization was successfully applied in the synthesis of functional β-ketoenamine-linked COFs of BTTP-TAPT and BTTP-TABPT in as short as 2 h. The resultant COFs exhibited highly efficient and selective adsorption of Au(III), with maximum adsorption capacities of 1847 and 1509 mg g –1, respectively. Additionally, when exfoliated into nanosheets and blended in a rigid poly(methyl methacrylate) matrix, they displayed remarkable ultralong organic room-temperature phosphorescence, with the lifetime of up to 695 ms. This synthesis method, characterized by its simplicity, rapidity, and atom economy, provides a green and sustainable alternative for the efficient synthesis of functional COFs.