Chemical Control over Nucleation and Anisotropic Growth of Two-Dimensional Covalent Organic Frameworks

[Image: see text] Two-dimensional covalent organic frameworks (2D COFs) are composed of structurally precise, permanently porous, layered polymer sheets. 2D COFs have traditionally been synthesized as polycrystalline aggregates with small crystalline domains. Only recently have a small number of 2D COFs been obtained as single crystals, which were prepared by a seeded growth approach via the slow introduction of monomers, which favored particle growth over nucleation. However, these procedures are slow and operationally difficult, making it desirable to develop polymerization methods that do not require the continuous addition of reactants over days or weeks. Here, we achieve the rapid growth of boronate ester-linked COFs by chemically suppressing nucleation via addition of an excess of a monofunctional competitor, 4-tert-butylcatechol (TCAT), into the polymerization. In situ X-ray scattering measurements show that TCAT suppresses colloid nucleation, which enables seeded growth polymerizations in the presence of high monomer concentrations. Kinetic Monte Carlo simulations reveal that TCAT limits oligomers to sizes below the critical nucleus size and that in-plane expansion is restricted compared to out-of-plane oriented attachment of oligomers. The simulations are consistent with transmission electron micrographs, which show that the particles grow predominantly in the stacking direction. This mechanistic insight into the role of the modulators in 2D polymerizations enables the size and aspect ratio of COF colloids to be controlled under operationally simple conditions. This chemically controlled growth strategy will accelerate the discovery and exploration of COF materials and their emergent properties.