Single-crystalline covalent organic frameworks directed by π-stacking

π-π Interactions are foundational to the stability of layered materials, yet their use as structure-directing forces in three-dimensional covalent organic frameworks (COFs) has remained unexplored. Here we employ a dihydropentacene (DHP)-based linker whose V-shaped geometry endows high solubility, conformational rigidity, and an exposed π-surface that directs the growth of singlecrystalline 3D COFs. Using DHP as a π-stacking module, we synthesized a series of single crystalline frameworks in which the parallel-displaced stacking of the acene cores stabilizes the extended architecture. This stacking mode persists despite reductions in node symmetry and electronic alteration of DHP core to incorporate heteroatoms. The resulting COFs exhibit robust, permanently porous structures with ultrahigh surface areas >5000 m 2 g-1 and thermal stability to 400 °C. These results establish πstacking as a general design principle for directing crystallization and structural order in 3D COFs.