Catenated covalent organic frameworks constructed from polyhedra

Although the synthetic chemistry leading to interlocking molecular [n]catenanes of organic polyhedra (n = 2–3) and rings (n = 2–130) is established, the analogous chemistry that pertains to infinite three-dimensional systems ([∞]catenane) remains undeveloped. We report a series of [∞]catenane covalent organic frameworks (termed catena-COFs). These were synthesized by linking 4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde to either of tris-(4-aminophenyl)-amine, -methane or -methanol through imine condensation. These combinations give discrete adamantane-like polyhedra, catenated by virtue of the copper(I) ions templating a mutually embracing arrangement of PDBs (points-of-catenation), which ultimately results in infinite catena-COF-805, 806 and 807. The crystal structures of these COFs obtained from electron microscopy and X-ray diffraction were determined to be isoreticular and to adopt the bor-y structure type.