Modular Donor–Acceptor Pairing Strategy Manipulating Weaving of Covalent Organic Polymer Crystals

Weaving or orderly stacking one‐dimensional chains endow covalent organic polymers (COPs) with attractive physical and chemical properties. However, harnessing interpretable design principles to drive and regulate the spontaneous entanglement of single molecular chains remains a significant challenge. In this study, inspired by the friction in macroscopic textiles, we propose a modular strategy to manipulate weaving through constructing donor–acceptor interdigitated covalent organic chains and tuning their twisting angles. To validate its soundness and feasibility, we synthesized three crystalline COPs (p‐BNF, m‐BNF, and p‐MeBNF) as exemplars with chemically similar main chains, yet distinct weaving or stacking patterns, which bestows them with varying organic semiconductor and mechanical properties. This work provides a promising strategy for the development of woven crystalline COPs and highlights the unique opportunities for delicate controls in semiconductors, mechanical materials and other scenes through weaving‐topology based strategies.