Supramolecular catalysis aims to mimic the high efficiency and specificity of natural enzymes, and coordination cages have emerged as one of the most active and promising directions in this field due to their tunable nano-cavities. Thiacalix[4]arenes and their oxidized derivatives, sulfonylcalix[4]arenes, are a class of “preorganized” macrocyclic ligands with a unique cone conformation and multiple coordination sites. They can assemble with transition metal ions to form well-defined, highly stable polynuclear cluster secondary building units (SBUs). Based on this “thia-/sulfonyl-calix[4]arene-metal cluster” motif and employing various polycarboxylate bridging linkers, various coordination cages with diverse topologies and tunable dimensions have been successfully constructed. By virtue of this type of coordination supramolecular cages, researchers have developed several catalytic functionalization strategies, including exploiting the cavity confinement effect, introducing active sites into the cage backbone, and encapsulating catalytic guest species. These strategies have enabled a wide range of complex chemical transformations, from simple model reactions to asymmetric synthesis, photo/electrocatalysis, and cascade reactions. This review systematically summarizes the latest research progress on thia-/sulfonyl-calix[4]arene-based coordination cages in catalysis. It specifically analyzes the paradigm shift in this field from “relying on mere physical confinement” toward “rationally designed cooperative catalysis,” with a particular emphasis on the design principles underlying enhanced catalytic selectivity and efficiency. Finally, the review provides perspectives on future directions for this field.

Key words: coordination cages, sulfonylcalix[4]arenes, supramolecular catalysis, cooperative catalysis