Precise control over topologically intricate molecular architectures remains an open challenge for chemists due to their inherent structural complexity. We report a simple solvent-free strategy to selectively prepare two multi-component supramolecular crystalline systems based on the halogen bond, endowed with either an unknot topology or a Borromean-type entanglement. Real-time in situ monitoring of the solvent-free mechanochemical synthesis of these three-component halogen-bonded ionic co-crystals reveals that the choice of milling conditions leads to a switch in the supramolecular reaction trajectory, resulting in the selective formation of an open halogen-bonded network or a halogen-bonded Borromean-type assembly.

由于其固有的结构复杂性，对拓扑复杂的分子结构的精确控制仍然是化学家的一个公开挑战。我们报告了一种简单的无溶剂策略，可选择性地基于卤素键制备两个多组分超分子晶体系统，这些系统具有不整齐的拓扑结构或Borromean型缠结。这些三组分卤素键合离子共晶体的无溶剂机械化学合成的实时原位监测表明，研磨条件的选择会导致超分子反应轨迹的转变，从而选择性地形成开放的卤素键网络或卤素键的Borromean型装配体。