Dynamic Cleavage‐Remodeling of Covalent Organic Networks into Multidimensional Superstructures

Abstract Superstructures with complex hierarchical spatial configurations exhibit broader structural depth than single hierarchical structures and the associated broader application prospects. However, current preparation methods are greatly constrained by cumbersome steps and harsh conditions. Here, for the first time, a concise and efficient thermally responsive dynamic synthesis strategy for the preparation of multidimensional complex superstructures within soluble covalent organic networks (SCONs) with tunable morphology from 0D hollow supraparticles to 2D films is presented. Mechanism study reveals the thermally responsive dynamic “cleavage‐remodeling” characteristics of SCONs, synthesized based on the unique bilayer structure of (2.2)paracyclophane, and the temperature control facilitates the process from reversible solubility to reorganization and construction of superstructures. Specifically, during the process, the oil–water‐emulsion two‐phase interface can be generated through droplet jetting, leading to the preparation of 0D hollow supraparticles and other bowl‐like complex superstructures with high yield. Additionally, by modulating the volatility and solubility of exogenous solvents, defect‐free 2D films are prepared relying on an air–liquid interface. Expanded experiments further confirm the generalizability and scalability of the proposed dynamic “cleavage‐remodeling” strategy. Research on the enrichment mechanism of guest iodine highlights the superior kinetic mass transfer performance of superstructural products compared to single‐hierarchical materials.