Cooperative Synthesis of Raspberry-Like Covalent Organic Framework-Polymer Particles with a Radial Single-Crystal Grain Orientation.

Despite many efforts devoted toward the design of covalent organic frameworks (COFs) at the framework level by selecting the building blocks, their organization in the nano to meso regimes is often neglected. Moreover, the importance of processability for their applications has recently emerged and the synthesis of COF nanostructures without agglomeration is still a challenge. Herein, the first example of hybrid COF-polymer particles for which polymers are used to manipulate the 2D COF growth along a specific direction is reported. The study examines how the nature, chain-end functionality, and molar mass of the polymer influence the shaping of hybrid 2D boronate ester-linked COF-polymer particles. Catechol-poly(N-butyl acrylate) leads to the self-assembly of crystallites into quasi-spherical structures while catechol-poly(N-isopropylacrylamide) mediates the synthesis of raspberry-like COF-polymer particles with radial grain orientation. Scanning and transmission electron microscopies (SEM and TEM) and 4D-STEM-ACOM (automated crystal orientation mapping) highlight the single-crystal character of these domains with one plane family throughout the particles. Interestingly, the presence of PNIPAm on the particle surface allows their drying without co-crystallization and enables their resuspension. Kinetic investigations show that catechol-PnBuA acts as a modulator and catechol-PNIPAm induces a template effect, introducing supramolecular self-assembly properties into particles to create new morphologies with higher structural complexity, beyond the framework level.