Functional Supramolecular Aggregates From Cavitands Based on Resorcin[4]Arene: Assembly and Applications

ABSTRACT Supramolecular aggregates, formed through the highly directional and reversible noncovalent assembly of building blocks, represent a cornerstone of modern materials science, enabling the creation of complex architectures with emergent properties. Among the diverse molecular platforms available, resorcin[4]arene‐derived cavitands have emerged as particularly powerful building units due to their intrinsic concave cavity, tunable geometry, and versatile functionalization capacity. This review highlights recent progress in the construction of functional supramolecular aggregates based on resorcin[4]arene cavitands, with a focus on their assembly strategies and wide‐ranging applications. The review systematically covers several key types of aggregate systems: porous coordination aggregates (e.g., metal‐organic frameworks [MOFs]) with stimuli‐responsive properties, dynamic polymeric aggregates exhibiting self‐healing behavior, sensing aggregates enabling differential detection, and therapeutic aggregates for combination therapy. These systems are unified by their exploitation of cavitands’ unique host‐guest chemistry and their ability to form well‐defined superstructures through various noncovalent interactions. We emphasize how the precise manipulation of cavitand structure directs the assembly process and dictates the functional output of the resulting aggregates. Finally, we outline current challenges and future opportunities in this field, highlighting the potential of cavitand‐based aggregates to enable next‐generation technologies in sensing, catalysis, biomedicine, and energy materials. This review is expected to provide valuable insights and inspiration for researchers working in supramolecular chemistry and aggregate science. The construction of supramolecular aggregates triggered by macrocycles has become a thriving area of supramolecular chemistry. In this context, resorcinarene cavitands, a class of macrocyclic receptors with intrinsic cavities, have been drawn into the limelight because of their advantages, such as the concave‐shaped structure, adjustable cavity size, favorable host‐guest behavior, and ease of functionalization. They can induce organic and inorganic molecules to self‐assemble into supramolecular aggregates through various bonding modes, including hydrophobic interactions, metal‐ligand coordination, van der Waals forces, hydrogen bonding, electrostatic interactions, π‐π stacking, and amphiphilic interactions. This minireview focuses on some representative resorcinarene cavitand‐based assembly aggregates, including microporous MOFs, supramolecular polymers, sensor arrays, and multifunctional nanodrugs. Each section highlights recent advancements, structural characteristics, and functional applications of these aggregate systems. This review will provide useful information for researchers working on not only cavitand chemistry but also the chemistry of other macrocyclic hosts, and it will inspire new discoveries in the field of supramolecular assemblies and systems containing macrocyclic hosts.