Supramolecular catalysis with emerging, functional organic macrocycles and cages.

Abstract

The development of supramolecular chemistry has provided both conceptual inspiration and a diverse array of host scaffolds for boosting catalytic processes, thereby driving the ongoing advancement of supramolecular catalysis. Among these, covalent organic hosts are particularly notable for their structurally robust scaffolds, which not only confer stability but also allow for extensive synthetic modification and the tailored incorporation of diverse functional groups. Beyond traditional privileged macrocyclic hosts-such as cyclodextrins, crown ethers, calixarenes, and cucurbiturils, which have long served as foundational supramolecular vessels-emerging functional organic macrocycles and molecular cages represent novel host platforms and exemplify new design paradigms. By orchestrating multiple noncovalent interactions within well-defined, confined cavities, these architectures could offer new opportunities to promote catalytic innovation and expand the frontiers of supramolecular catalysis. In this review, we focus primarily on recent advances in the use of emerging functional organic macrocycles and cages for boosting catalytic processes. The discussion begins with covalent organic macrocycles, which are broadly classified into three categories: hydrogen-bonding-type macrocycles, cation-binding-type macrocycles, and π-receptor-type macrocycles. This is followed by a discussion of functional organic cage-based catalytic systems. Finally, we examine macrocyclic and cage architectures that incorporate active metal centers. Particular emphasis is placed on how these architectures leverage spatial confinement and synergistic interactions to facilitate chemical transformations, ultimately achieving high catalytic efficiency, enhanced selectivity, and novel reactivity profiles.