Beyond Cocrystals: Hierarchical Functional Assemblies via Noncovalent Synthesis

ABSTRACT Cocrystals are solid crystals formed by the combination of multiple components through non‐covalent interactions (NCIs). Despite their diverse structures and tunable optoelectronic properties, they cannot meet the demand for multi‐functionalization of optoelectronic devices. Therefore, a series of strategies is summarized to construct organic hierarchical structures (OHSs) by self‐assembly of NCIs using organic cocrystals as base building blocks. Sequential nucleation of cocrystals has been achieved by regulating the strength of NCIs to further synthesize complex OHSs. This review explores the fundamental factors affecting the physicochemical properties of cocrystals, such as molecular arrangement, the distance and orientation of intermolecular interactions, etc. Additionally, the self‐assembly process of synthetic OHSs driven by single & multiple NCIs is analyzed, along with the applications of these structures in optoelectronics. Finally, urgent issues on preparing OHSs are raised, and an outlook on possible future opportunities is provided.