Facile Synthesis of a Fully Fused, Three-Dimensional π-Conjugated Archimedean Cage with Magnetically Shielded Cavity

摘要

The synthesis of molecular cages consisting of fully fused, π-conjugated rings is rare due to synthetic challenges including preorganization, large strain, and poor solubility. Herein, we report such an example in which a tris-2-aminobenzophenone precursor undergoes acid-mediated self-condensation to form a truncated tetrahedron, one of the 13 Archimedean solids. Formation of eight-membered [l,5]diazocine rings provides preorganization and releases the strain while still maintains weak π-conjugation of the backbone. Thorough characterizations were performed by X-ray, NMR, and UV-vis analysis, assisted by theoretical calculations. The cage exhibits a rigid backbone structure with a well-defined cavity that confines a magnetically shielded environment. The solvent molecule, o-dichlorobenzene, is precisely encapsulated in the cavity at a 1:1 ratio with multiple π…π, C-H…n, and halogen…π interactions with the cage skeleton, implying its template effect for the cage closing reaction. Our synthetic strategy opens the opportunity to access more complex, fully fused, three-dimensional π-conjugated cages.