ALT Porphyrin atropisomerism is an outstanding tool for the accessibility of shape-specific molecules. There is a growing need to control this phenomenon in nonplanar porphyrin systems due to the mounting interest in these systems as enzyme mimics and organocatalysts. Hence, in this work, the influence of steric bulk on the stability of nonplanar 5,10,15,20-tetraaryl-2,3,7,8,12,13,17,18-octaethyl-porphyrin atropisomers was explored. The library of atropisomeric porphyrins synthesized herein emphasizes the delicate balance that must be achieved between steric bulk without inducing an undesired amount of macrocycle flexibility to obtain an atropisomer with a predictable rotational barrier. To overcome this challenge, a stabilization strategy was devised by exploiting metal coordination to the peripheral porphyrin functionalities, leading to an atroposelective superstructure formation.

ALT Chiral self-assembled supramolecular networks offer great potential for new chiral materials. We report the predictable self-assembly of metalloporphyrins with chiral cyclohexanohemicucurbit[n]urils (cycHC[6] and cycHC[8]), where cycHC[n] chirality is transferred to achiral porphyrins in solution and the solid state. Solvent and porphyrin substituents directed the formation of 31 novel complexes characterized by single-crystal X-ray diffraction. All complexes feature metal–urea coordination centers, with architectures ranging from discrete complexes to 1D, helical 1D, and 2D square-grid coordination polymers, governed by the shape and binding strength of cycHC[n]s. These results demonstrate the robustness of hemicucurbituril–metalloporphyrin supramolecular systems for developing advanced chiral sensing materials.