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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.