This paper discloses coordination approaches to well-defined organic structures including macrocycles, a three-dimensional cage-like compound, and [2]catenanes. These supramolecules self-assembled from (en)Pd(NO 3 ) 2 (1, en = ethylenediamine) and appropriate polypyridyl-substituted ligands. Treatment of 1 with 4,4 -bipyridine (2), for example, gave the macrocyclic tetranuclear Pd(II) complex [(en)Pd(μ-2)] 4 (NO 3 ) 8 quantitatively, while macrocyclic dinuclear Pd(II) complexes were assembled from 1 and flexible ligands such as PyCH 2 CH 2 Py (Py = 4-pyridyl). From the tridentate ligand 1,3,5-(PyCH 2 ) 3 C 6 H 3 and 1 in 2:3 ratio, however, a three-dimensional cage-like compound was assembled in high yields only in the presence of certain types of guest molecules, providing an entire model for induced-fit . The coordination approach made it possible to interlock two apparently continuous molecular rings: i.e. a macrocycle assembled from 1 and 1,4-(PyCH 2 ) 2 C 6 H 4 was found to exist in equilibrium with its catenated dimer, and a polar medium strongly pushed the equilibrium toward the catenane up to a greater than 99:1 ratio.