Directing metallo-supramolecular assembly through complementarity

In chemistry, function and behaviour flow directly from structure. As chemists seek to develop highly complex functional molecules, we need to harness routes to complex structures. In metallosupramolecular self-assembly, this requires the development of strategies to overcome the tendency of self-assembled systems to be either (1) highly symmetric in the presence of a single ligand type, or (2) statistical equilibrium mixtures in the presence of multiple ligands. This Feature Article describes our efforts to enforce control for the formation of highly ordered and defined architectures that are either low symmetry or comprise lower symmetry components. We have used complementary and orthogonal arrangements of ligands at the metal ion site to control connectivity, with additional conformational or geometric regulation arising through π-π interactions.