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. [ABSTRACT FROM AUTHOR]