Triphenylamine[3]arenes: Streamlining Synthesis of a Versatile Macrocyclic Platform for Supramolecular Architectures and Functionalities

Abstract Triphenylamine[3]arenes (TPA[3]s), featuring [16]paracyclophane backbone with alternating carbon and nitrogen bridging atoms, were synthesized through a BF3 ⋅ Et2O‐catalyzed cyclization reaction using triphenylamine derivatized monomers and paraformaldehyde. This molecular design yielded a series of TPA[3] macrocycles with high efficiency, with their facile derivatizations also successfully demonstrated. On account of the strong electron‐donating properties of the TPA moieties, these TPA[3]s exhibit remarkable delayed fluorescence, and possess a significant affinity for iodine. Furthermore, their inherent three‐fold symmetry rendered TPA[3]s as novel building blocks for the construction of extended frameworks and molecular cages. This advancement expands the versatility of discrete macrocycles into complex architectures, enhancing their applicability across a broad spectrum of applications.