Self-recognition and self-selection in multicomponent supramolecular coordination networks on surfaces

Self-recognition, self-selection, and dynamic self-organization are of fundamental importance for the assembly of all supramolecular systems, but molecular-level information is not generally accessible. We present direct examples of these critical steps by using scanning tunneling microscopy to study mixtures of complementary organic ligands on a copper substrate. The ligands coordinate cooperatively with iron atoms to form well ordered arrays of rectangular multicomponent compartments whose size and shape can be deliberately tuned by selecting ligands of desired length from complementary ligand families. We demonstrate explicitly that highly ordered supramolecular arrays can be produced from redundant ligand mixtures by molecular self-recognition and -selection, enabled by efficient error correction and cooperativity, and show an example of failed self-selection due to error tolerance in the ligand mixture, leading to a disordered structure.