Three-Dimensional Large-Pore Covalent Organic Framework with Stp Topology

Three-dimensional (3D) covalent organic frameworks (COFs) are excellent porous crystalline polymers for numerous applications, but their building units and topological nets have been limited. Herein we report the first 3D large-pore COF with stp topology constructed with a 6-connected triptycene-based monomer. The new COF (termed JUC-564) has high surface area (up to 3300 m 2 g -1 ), the largest pore (43 Å) among 3D COFs, and record-breaking low density in crystalline materials (0.108 g cm -3 ). The large pore size of JUC-564 is confirmed by the incorporation of a large protein. This study expands the structural varieties of 3D COFs as well as their applications for adsorption and separation of large biological molecules.