Stepwise Self‐Assembly and Dynamic Exchange of Supramolecular Nanocages Based on Terpridine Building Blocks

Coordination‐driven self‐assembly as a powerful bottom‐up approach has been extensively used to construct multifarious supramolecular architectures with increasing complexity and functionality. Due to the unique cavity structures and precisely controllable dimensions, 3D supramolecules display unprecedented properties and functions in catalysis, sensing, gas storage, and smart materials. Herein, we have built two 3D nanocages with different sizes by changing the length of the organic ligand arms. The structures were characterized by 1D and 2D NMR spectroscopy, electrospray ionization‐mass spectrometry (ESI‐MS), traveling wave ion mobility‐mass spectrometry (TWIM‐MS), gradient tandem‐mass spectrometry (gMS2), and transmission electron microscopy (TEM). Furthermore, the intermolecular dynamic exchange of two 3D nanocages was conducted to construct a series of hybrid 3D structures as evidenced by mass spectrometry. Two 3D nanocages with different sizes are assembled successfully by a stepwise approach. The further dynamic ligand exchange between two preassembled nanocages generated as a series of hybrid supramolecular nanocages, suggesting the remarkable tolerance of such structures with different edge length. The rapid communication between supramolecules via ligand exchange further increased the complexity of the system.