The supramolecular coordination of zinc (II) phthalocyanine (Zn-Pc) with V-shaped bi-pyridine in a nano-reactor is probed by scanning tunneling microscopy (STM) at liquid/solid interface. Combined with density functional theory (DFT) calculations, our STM results show that the V-shaped bi-pyridine and Zn-Pc can generate stable “odd-even” patterned architectures in the TCDB network through a two-step coordination process. Moreover, great changes for the size and the shape of the host cavity have happened during the coordination process. In general, the whole coordination process is regulated by the synergies of ligand and template. To the best of our knowledge, this is the first work on imaging of supramolecular coordination in a nano-reactor. Such a template-regulated supramolecular interconversion opens a new avenue towards the crystal engineering and design as well as the generation of controllable nano-patterns.

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