Synthetic routes to the crystallization of two new box-like complexes, [Au(Triphos)(CuBr)](OTf)·(CHCl)·(CHOH)·(HO) () and [Au(Triphos) (CuCl)](PF)·(CHCl) () (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine), have been developed. The two centrosymmetric cationic complexes have been structurally characterized through single-crystal X-ray diffraction and shown to contain a CuX (X = Br or Cl) unit suspended between two Au(I) centers without the involvement of bridging ligands. These colorless crystals display green luminescence (λ = 527 nm) for () and teal luminescence (λ = 464 nm) for (). Computational results document the metallophilic interactions that are involved in positioning the Cu(I) center between the two Au(I) ions and in the luminescence.
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