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 PdII and PtII 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 PdII -rich fiber-like co-assemblies by a statistical co-nucleation event along with a residual amount of self-sorted nanodisks in a stepwise manner.