Guest-programmed adaptive reconfiguration in heteroleptic metal–organic cages

<jats:p>Adaptive reconfiguration of complex supramolecular assemblies remains a fundamental challenge in synthetic chemistry, especially for heteroleptic systems prone to kinetic traps and component scrambling. Here we report a guest-cooperative reassembly strategy that enables programmable cage-to-cage transformation in heteroleptic pentagonal prismatic ZnII cages, assembled via precise edge-length matching between pentatopic and tetratopic ligands. Distinct from conventional single-guest templation, these cages exhibit transformation behavior governed by cooperative multi-guest interactions within confined cavities. Chlorinated guests are selectively encapsulated through Cl···π and π···π interactions, thereby biasing the thermodynamic landscape of assembly. Secondary guests trigger distinct and predictable transformation pathways, including guest release, guest exchange, or stoichiometrydependent reassembly into a homoleptic pseudo-cubic cage with one or two encapsulated guests. Crystallographic, Hirshfeld surface and computational analyses reveal that multiple Cl···π, π···π, and C–H···π noncovalent interactions within the confined cavity govern the transformation selectivity. Furthermore, the incorporation of peripheral pyrene units imparts the prismatic cages with photoluminescence, which is enhanced upon guest binding due to framework rigidification. This work establishes a generalizable design principle whereby confined multi-guest interactions direct thermodynamically controlled reconfiguration of complex heteroleptic assemblies, providing a foundation for programmable adaptive supramolecular systems.</jats:p>