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Combining the star‐shaped alkynyl ligands with low‐nuclearity gold–copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φem=0.6). Their luminescence mainly originates from cluster‐localized metal‐to‐ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold‐silver...
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