2026 Volume 87 Pages 41-48
Discrete stacked complexes constructed from planar and macrocyclic molecules have emerged as versatile platforms for precise molecular organization and exploration of their functions. This review summarizes recent advances in the design and construction of such complexes based on coordination-driven self-assembly. Three representative strategies are highlighted: (i) Metal-mediated sandwich stacking, (ii) pillared architectures using bridging organic ligands, and (iii) self-complementary stacking driven by intermolecular coordination. These approaches enable precise control over stacking number, interplanar distance, and the spatial arrangement of metal centers and coordination sites. As a result, a variety of discrete assemblies with well-defined molecular stacking and/or internal spaces have been realized. These confined environments provide unique opportunities for molecular recognition, selective catalysis, and photofunctional processes, often through cooperative interactions such as multipoint coordination and aromatic interactions. In addition, recent studies demonstrate dynamic control of stacking structures triggered by external stimuli or guest molecules, expanding the scope of functional design. The concepts and strategies discussed herein offer useful guidelines for constructing sophisticated supramolecular architectures and are expected to inspire future developments in coordination chemistry and functional molecular systems.
