Manipulation of Covalent Organic Frameworks by Side-Chain Functionalization: Toward Few Layer Nanosheets

Recent developments in the field of covalent organic frameworks (COFs) describe the issue of processability. The precise tunability of delamination of such structures to obtain few layered nanosheets by synthetic control has been ventured in this study. Covalent anchoring of a series of linear and branched alkoxy side chains to the backbone of layered covalent organic frameworks was used to achieve this. To support the hypothesis, powder X-ray diffraction studies accompanied by computational modeling revealed that the elongation of side chains increases the interlayer distances of the COFs. This led to a successful study of the solvent-assisted exfoliation by atomic force microscopy techniques to obtain nanosheets with heights less than 2 nm, representing stacks of 4–5 layers. Dispersions of the functionalized COF nanosheets are stable for several hours. Furthermore, the surface properties are drastically changed, rendering the materials hydrophobic, with contact angles reaching up to 142° and complete blockage of the pore space toward water vapor. As a proof of concept, the sheets are processable and could be integrated into separators for lithium-ion batteries.