Unsupported Au(I)...Cu(I) interactions: influence of nitrile ligands and aurophilicity on the structure and luminescence.
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.
Fernández
Eduardo J
EJ
Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC. Complejo Científico-Tecnológico, 26004-Logroño, Spain.
Laguna
Antonio
A
López-de-Luzuriaga
José M
JM
Monge
Miguel
M
Montiel
Manuel
M
Olmos
M Elena
ME
Rodríguez-Castillo
María
M