Shape‐Controlled Synthesis and Self‐Sorting of Covalent Organic Cage Compounds

The directional bonding approach is a powerful tool to rationally control both shape and stoichiometry of three‐dimensional objects built from rigid building blocks under dynamic covalent conditions. Co‐condensation of catechol‐functionalized tribenzotriquinacene derivatives which have 90° angles between the reactive sites and diboronic acids with bite angles of 60°, 120°, and 180°, led to the efficient formation of, respectively, bipyramidal, tetrahedral, or cubic covalent organic cage compounds in a predictable manner. Investigations on the self‐sorting of ternary mixtures containing two competitive boronic acids revealed either narcissistic or social self‐sorting depending on the stability of the segregated cages relative to feasible three‐component assemblies.