Programmable Multicomponent Self‐Assembly Based on Aromatic Amino Acids

Abstract Construction of integrated self‐assembly with ordered structures from two or more organic building blocks is currently a challenge, since it suffers from intrinsic systematic complexity and diverse competitive pathways. Here, it is reported that aromatic amino acid building units can be incorporated into two‐ or three‐component coassembly driven primarily by hydrogen bonding interactions without the assistance of metal–ligand and macrocycle‐based host–guest interactions. The key strategy is to employ a C₃‐symmetric molecule with alternative hydrogen bonding donor/acceptor sites that are able to bind either carboxylic acid or pyridine appended building units. Aromatic amino acids, C₃‐symmetric compound, and bipyridine unit constitute a unique ternary mutual binding system, where three coassembly pathways including two pairwise formations and one ternary combination are unveiled, giving rise to two‐ and three‐component self‐assemblies with ordered structures, respectively. The pathway complexity lies in the structural parameter of aromatic amino acids, which can be programmable by controlling substituents at the α‐position of amino acids.