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Treasure chests: The Group 11 metals CuI, AgI, and AuI form tetrahedral supramolecular clusters with a rigid threefold‐symmetric phosphine ligand. These supramolecular clusters, which assemble by metal–phosphine interactions, are the first to form across an entire group of the periodic table. Cu+ green, Ag+ pale blue, Au+ green, I− red, P purple.
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