Synergizing Steric Hindrance and Stacking Interactions to Facilitate the Controlled Assembly of Multiple 41 Metalla‐Knots and Pseudo‐Solomon Links

In this work, a noncoplanar terphenyl served as building block to synthesize a novel 3,3'‐substituted bipyridyl ligand (L1) which further reacted with binuclear half‐sandwich units A/B, giving rise to two aesthetical 41 metalla‐knots in high yields via coordination‐driven self‐assembly strategy. Furthermore, given the inherent compactness of the 41 metalla‐knots, it creates favorable conditions for the emergence of steric repulsion. We focused on progressively introducing nitrogen atoms featuring lone pair electrons (LPEs) into ligand L1 to manipulate the balance of H···H/LPEs···LPEs steric repulsion during the assembly process, ultimately achieving controlled assembly from 41 metalla‐knots to the pseudo‐Solomon link and then to molecular tweezer‐like assembly facilitated by stacking interactions. All the assemblies were well characterized by solution‐state NMR techniques, ESI‐TOF/MS, and single‐crystal X‐ray diffraction. The evolutionary process of topological architectures is equivalent to visualizing the synergistic effect of steric hindrance and stacking interactions on structural assembly, providing a new avenue for achieving the controlled synthesis of different topologies.