The reticular synthesis of covalent organic frameworks (COFs), extended porous two-dimensional (2D) or three-dimensional (3D) networks held together by strong, highly directional chemical bonds, has thus far been restricted to small, shape-persistent, molecular building blocks. Here, we demonstrate the growth of crystalline 2D COFs from a polydisperse macromolecule derived from single-layer graphene, bottom-up synthesized quasi-one-dimensional (1D) graphene nanoribbons (GNRs). X-ray scattering and transmission electron microscopy reveal that 2D sheets of GNR-COFs self-assembled at a liquid-liquid interface stack parallel to the layer boundary and exhibit an orthotropic crystal packing. Liquid-phase exfoliation of multilayer GNR-COF crystals gives access to large-area (>10⁵ nm²) bilayer and trilayer cGNR-COF films. The functional integration of extended 1D materials into crystalline COFs greatly expands the structural complexity and the scope of mechanical and physical materials properties accessible through a deterministic reticular bottom-up approach.

到目前为止，共价有机骨架（COF）的网状合成，扩展的多孔二维（2D）或三维（3D）网络通过牢固的，高度方向性的化学键结合在一起，目前仅限于小的，形状持久的分子建筑模块。在这里，我们证明了从单层石墨烯，自底向上合成的准一维（1D）石墨烯纳米带（GNR）衍生的多分散大分子中结晶2D COF的生长。X射线散射和透射电子显微镜显示，GNR-COF的二维薄片在液-液界面处平行于层边界自动组装，并表现出正交各向异性晶体堆积。多层GNR-COF晶体的液相剥落可进入大面积区域（> 10 ⁵ nm ²）双层和三层cGNR-COF薄膜。扩展的一维材料到晶体COF的功能集成极大地扩展了结构的复杂性，并通过确定性的网状自下而上的方法获得了机械和物理材料特性的范围。