Nucleation–Elongation Dynamics of Two-Dimensional Covalent Organic Frameworks

2020 
Homogeneous two-dimensional (2D) polymerization is a poorly understood process in which topologically planar monomers react to form planar macromolecules, often termed 2D covalent organic frameworks (COFs). While these COFs have traditionally been limited to weakly crystalline aggregated powders, they were recently grown as micron-sized single crystals by temporally resolving the growth and nucleation processes. Here, we present a quantitative analysis of the nucleation and growth rates of 2D COFs via kinetic Monte Carlo (KMC) simulations using COF-5 as an example, which show that nucleation and growth have second-order and first-order dependences on monomer concentration, respectively. The computational results were confirmed experimentally by systematic measurements of COF nucleation and growth rates performed via in situ X-ray scattering, which validated the respective monomer concentration dependencies of the nucleation and elongation processes. A major consequence is that there exists a threshold mon...
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