title: Unsupported Au(I)...Cu(I) interactions: influence of nitrile ligands and aurophilicity on the structure and luminescence.
abstract: The synthesis, structural characterization and the study of the photophysical properties of complexes [AuCu(C6F5)2(N[triple bond]C-CH3)2] 1, [AuCu(C6F5)2(N[triple bond]C-Ph)2]2 2, and [AuCu(C6F5)2(N[triple bond]C-CH=CH-Ph)2] 3 have been carried out. The crystal structures of complexes 1-3 consist of dinuclear Au-Cu units built from mediated metallophilic Au(I)...Cu(I) interactions. In the case of complex 2 two dinuclear units interact via an aurophilic interaction leading to a tetranuclear Cu-Au-Au-Cu arrangement. Complex 2 is brightly luminescent in solid state at room temperature and at 77 K with a lifetime in the nanoseconds range, while complexes 1 and 3 do not display luminescence under the same conditions. The presence of the aurophilic interaction in complex 2 seems to be responsible for the blue luminescence observed. DFT and time-dependent DFT calculations agree with the experimental results and support the idea that the origin of the luminescence of these complexes arise from orbitals located in the interacting metals.
authors.affiliation: Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC. Complejo Científico-Tecnológico, 26004-Logroño, Spain.
authors.forename: Eduardo J
authors.initials: EJ
authors.lastname: Fernández
authors.forename: Antonio
authors.initials: A
authors.lastname: Laguna
authors.forename: José M
authors.initials: JM
authors.lastname: López-de-Luzuriaga
authors.forename: Miguel
authors.initials: M
authors.lastname: Monge
authors.forename: Manuel
authors.initials: M
authors.lastname: Montiel
authors.forename: M Elena
authors.initials: ME
authors.lastname: Olmos
authors.forename: María
authors.initials: M
authors.lastname: Rodríguez-Castillo