Ketazine-Linked Crystalline Porous Covalent Organic Frameworks

Covalent organic frameworks (COFs) are a class of crystalline porous materials with well-defined π arrays and ordered channels, which can be predesigned with a topology diagram and prepared via a polycondensation reaction. Over the past decade, various types of π building units with different functional groups have been developed. Among them, aldehyde is one of the most widely used monomers that form COFs with azine, hydrazine, imine, squaranine, and C═C linkages. In contrast, its closest analogue, i.e., ketone, despite its broad structural diversity, has not yet been investigated for the design and synthesis of COFs. Herein we report the first examples of ketazine-linked COFs by developing ketones as monomers to enable polycondensation with hydrazine under solvothermal conditions. We observed that a careful screening of reaction conditions including solvent, catalyst, concentration, reaction temperature, and reaction time leads to the finding of optimal polymerization systems to produce highly crystalline and porous ketazine-linked COFs. Surprisingly, the ketazine linkage enables π conjugation between knot and linker sites and renders the resultant materials able to emit a strong blue fluorescence, highlighting the π electronic features of this new family of COFs. Our findings of ketones as monomers and ketazine as linkage bring unprecedented structures, functions, and applications to the field of COFs.