Self‐Assembly of Super‐Uniform Covalent Organic Framework Colloidal Particles into Multi‐Dimensional Ordered Superstructures

Abstract Precise self‐assembly of colloidal particles is crucial for understanding their aggregation properties and preparing macroscopic functional devices. It is currently very challenging to synthesize and self‐assemble super‐uniform covalent organic framework (COF) colloidal particles into well‐organized multidimensional superstructures. Here, simple and versatile strategies are proposed for synthesis of super‐uniform COF colloidal particles and self‐assembly of them into 1D supraparticles, 2D ordered mono/multilayers, and 3D COF films. For this purpose, several self‐assembly techniques are developed, including emulsion solvent evaporation, air‐liquid interfacial self‐assembly, and drop‐casting. These strategies enable the superstructural self‐assembly of particles of varying sizes and species without any additional surfactants or chemical modifications. The assembled superstructures maintain the porosity and high specific surface area of their building blocks. The feasibility of the strategies is examined with different types of COFs. This research provides a new approach for the controllable synthesis of super‐uniform COF colloidal particles capable of self‐assembling into multidimensional superstructures with long‐range order. These discoveries hold great promise for the design of emerging multifunctional COF superstructures.