A core feature of covalent organic frameworks (COFs) is crystallinity, but current crystallization processes rely substantially on trial and error, chemical intuition and large-scale screening, which typically require harsh conditions and low levels of supersaturation, hampering the controlled synthesis of single-crystal COFs, particularly on large scales. Here we report a strategy to produce single-crystal imine-linked COFs in aqueous solutions under ambient conditions using amphiphilic amino-acid derivatives with long hydrophobic chains. We propose that these amphiphilic molecules self-assemble into micelles that serve as dynamic barriers to separate monomers in aqueous solution (nodes) and hydrophobic compartments of the micelles (linkers), thereby regulating the polymerization and crystallization processes. Disordered polyimines were obtained in the micelle, which were then converted into crystals in a step-by-step fashion. Five different three-dimensional COFs and a two-dimensional COF were obtained as single crystals on the gram scale, with yields of 92% and above.

共价有机框架 (COF) 的一个核心特征是结晶度，但目前的结晶过程主要依赖于反复试验、化学直觉和大规模筛选，这通常需要苛刻的条件和低水平的过饱和度，阻碍了单分子的可控合成。晶体 COF，特别是在大尺度上。在这里，我们报告了一种在环境条件下使用具有长疏水链的两亲氨基酸衍生物在水溶液中生产单晶亚胺连接 COF 的策略。我们建议这些两亲性分子自组装成胶束，作为动态屏障来分离水溶液中的单体（节点）和胶束的疏水区室（接头），从而调节聚合和结晶过程。在胶束中获得无序聚亚胺，然后逐步将其转化为晶体。以克级单晶形式获得了五种不同的三维 COF 和二维 COF，产率为 92% 及以上。