Single-Crystalline Triptycene-Based Covalent Organic Frameworks

The crystallization of covalent organic frameworks (COFs) into single crystals remains a fundamental challenge, particularly beyond 4-connected tetrahedral nodes toward higher-connectivity building units. Here, we report the rapid synthesis of three tripty cene-based single-crystalline COFs (COF-563, -564, and -565) under mild conditions within 24 hours. By employing rigid 6-connected trigonal prismatic triptycene-based building units, hexakis(4-aminophenyl/4-formylphenyl)triptycene (Trip-NH 2/Trip-CHO), we access a topological regime of 3D COFs that includes the established hea and stp nets as well as an unprecedented (6,6)-connected htp topology. These frameworks are constructed through reticulation of the triptycene nodes with tetrahedral (tetra(4-anilyl)methane (TAM)), rectangular (pyrene-1,3,6,8-tetraaniline (PyTTA)), and hexagonal (hexakis(4′-formyl-[1,1′-biphenyl]-4-yl)benzene (HFBB)) complementary linkers to yield the hea, stp,