Mechanistic Insights into Statistical Co‐Assembly of Metal Complexes

Statistical copolymerization plays a key role in many biological and technological processes; however, mechanistic understanding of the formation of analogous supramolecular counterparts remains limited. Herein, we report detailed insights into the supramolecular co‐assembly of two π‐conjugated Pd(II) and Pt(II) complexes, which in isolation self‐assemble into flexible fibers and nanodisks, respectively. An efficient single‐step co‐assembly into only one type of nanostructure (fibers or nanodisks) takes place if any of the components is in excess. In contrast, equimolar mixtures lead to Pd(II)‐rich fiber‐like co‐assemblies by a statistical co‐nucleation event along with a residual amount of self‐sorted nanodisks in a stepwise manner.