Despite substantial advancements in the synthesis of mechanically interlocked molecules (MIMs), achieving the efficient construction of higher-order links remains a formidable challenge. Herein, we report the highly efficient one-step directed construction of a series of unprecedented molecular closed four-link chains (84 1 metalla-links), achieved through the synergistic assembly of coordination-driven and aromatic stacking interactions involving binuclear rhodium/iridium precursors and bidentate benzothiadiazole derivative ligands. Meanwhile, modulating the substituent positions of the pyridine groups in bidentate ligand resulted in a change in the topological structure, leading to the formation of two molecular Borromean links (63 2metalla-links). The molecular configurations of abovementioned metalla-links were clearly identified through mass spectrometry, NMR, and single-crystal X-ray diffraction. Furthermore, the structural transformation between the molecular Borromean links and corresponding monocycles was achieved through concentration effects, as validated by solution-state NMR spectroscopy investigations.