Spontaneous formation of the heteroleptic cadmium(II) bis(terpyridine) complex under ambient conditions can be achieved by a combination of 6,6''-di(2,6-dimethoxylphenyl)-substituted and unsubstituted terpyridine-based ligands. Building on this dynamic heteroleptic complexation, diverse metallo-supramolecular macrocycles and cages were readily assembled in quantitative yields from the predesigned multicomponent systems. The complementary ligation reinforced self-recognition to facilitate the shape-dependent self-sorting of a four-component dynamic library into two well-defined parallelograms. In addition, the subtle lability difference between homoleptic and heteroleptic complexes led to the site-selective Cd -Zn transmetalation in the Sierpiński triangle. Facile construction of a dodecanuclear tetrahedral metallocage was also realized by using two self-recognizable tritopic building blocks. The photophysical study of the metallo-supramolecules assembled from the d metal ions revealed intense ligand-based photoluminescence in solution. The self-assembly strategy described here provides an efficient methodology for building pre-programmable, sophisticated supramolecular architectures furnished with photoactivity.

Dynamic heteroleptic complexation of CdII ions with terpyridine ligands was used to construct 2D and 3D photoluminescent metallo‐supramolecules through multicomponent self‐assembly under mild conditions. The complementary ligand pair greatly enhanced self‐recognition between oligotopic ligands so that the self‐sorting of a four‐component dynamic library into two polygons was realized. The highly site‐selective CdII–ZnII transmetalation within a structurally preserved framework was achieved by the lability difference between homoleptic and heteroleptic complexes. More information can be found in the Full Paper by Y.‐T. Chan et al. on page 9274 ff.