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.