Supramolecular Copolymers Under Kinetic, Thermodynamic, or Pathway‐Switching Control

Supramolecular copolymers have attracted much attention due to their potential functionalities. However, the co-assembly strategies to construct co-assemblies of small molecules with well-defined sequence structures are still limited, especially for more complex crystalline block co-assemblies. Herein, we target this challenge by designing IrIII complexes 1 and 2, which possess unique self-assembly pathways and are capable of forming crystalline assemblies in aqueous systems. Specifically, block and random co-assemblies of 1 and 2 can be synthesized by kinetic and thermodynamic control, respectively. Meanwhile, by adjusting the water content to orthogonalize the on-pathway and the off-pathway, an unprecedented pathway-switching approach is realized to synthesize block and random co-assemblies. By coupling the kinetic pathways, the present co-assembly strategies are expected to pave the way for the synthesis of crystalline co-assemblies of small molecules and the construction of organic heterostructures.