From Binary to Higher‐Order Organic Cocrystals: Design Principles and Performance Optimization

Abstract

Abstract Organic cocrystals, particularly the evolution from binary to higher‐order structures, have garnered considerable attention due to their tunable intermolecular interactions and unique material properties. Binary cocrystals, formed through π‐π stacking, charge transfer, and hydrogen/halogen bonding, allow for precise control over molecular packing and enhanced optoelectronic properties. In contrast, higher‐order cocrystals, incorporating three or more components, enable greater complexity and functional diversity. Strategies such as homologation via isostructural substitution, hierarchical intermolecular interactions, and long‐range Synthon Aufbau Modules facilitate the synthesis of these advanced materials. The shift toward higher‐order cocrystals paves the way for novel applications in fields such as deep learning for cocrystal prediction, drug design, organic solar cells, and NIR‐II photothermal conversion. However, challenges related to molecular screening, ratio optimization, scalable synthesis, and long‐term stability remain critical hurdles for the broader implementation of these materials in practical applications.