Abstract
A novel gold(I)‐cluster‐based twin‐cage is constructed by post‐clustering covalent modification of a hexa‐aldehyde cluster precursor with triaminotriethylamines. The cages‐on‐cluster structure have double cavities and four binding sites, showing site discriminative binding for silver(I) and copper(I) guests. The guests in the tripodal hats affect the luminescence of the cluster: tetra‐silver(I) host‐guest complex is weak red emissive, while bis‐copper(I)‐bis‐silver(I) one is non‐emissive but a stimuli‐responsive supramolecule. The copper(I) ion inside the tri‐imine cavity is oxidation sensitive, which enable the release of the bright emissive precursor cluster triggered by H2O2 solution. The hybridization of a cluster with cavities to construct a cluster‐based cage presents an innovative concept for functional cluster design, and the post‐clustering covalent modification opens up new avenues of finely tuning the properties of clusters.
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