Self-Assembled Encapsulation of CuX2- (X = Br, Cl) in a Gold Phosphine Box-like Cavity with Metallophilic Au-Cu Interactions

Daniel T Walters; Michael M Aristov; Reza Babadi Aghakhanpour; Daniel J SantaLucia; Sarah Costa; Marilyn M Olmstead; John F Berry; Alan L Balch

doi:10.1021/acs.inorgchem.2c04067

Self-Assembled Encapsulation of CuX₂^- (X = Br, Cl) in a Gold Phosphine Box-like Cavity with Metallophilic Au-Cu Interactions

Inorg Chem. 2023 Mar 20;62(11):4467-4475. doi: 10.1021/acs.inorgchem.2c04067. Epub 2023 Mar 10.

Authors

Daniel T Walters¹, Michael M Aristov², Reza Babadi Aghakhanpour¹, Daniel J SantaLucia², Sarah Costa¹, Marilyn M Olmstead¹, John F Berry², Alan L Balch¹

Affiliations

¹ Department of Chemistry, University of California-Davis, One Shields Avenue, Davis, California 05616, United States.
² Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.

PMID: 36897254
DOI: 10.1021/acs.inorgchem.2c04067

Abstract

Synthetic routes to the crystallization of two new box-like complexes, [Au₆(Triphos)₄(CuBr₂)](OTf)₅·(CH₂Cl₂)₃·(CH₃OH)₃·(H₂O)₄ (1) and [Au₆(Triphos)₄ (CuCl₂)](PF₆)₅·(CH₂Cl₂)₄ (2) (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 CuX₂^- (X = Br or Cl) unit suspended between two Au(I) centers without the involvement of bridging ligands. These colorless crystals display green luminescence (λ_em = 527 nm) for (1) and teal luminescence (λ_em = 464 nm) for (2). 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.