AbstractThe ability to design and synthesize monomers can affect fundamental aspects in 2D covalent organic frameworks, such as dimensionality, topology, and pore size. Besides this, the structure of the monomers can also affect interlayer interactions, which provide an additional means to influence crystallinity, layer arrangement, interlayer distances, and exfoliability. Herein, some of the effects that the structure of monomers can have on the interlayer interactions in 2D covalent organic frameworks and related materials are illustrated.