The synthesis, structural characterization, and the study of the photophysical properties of complexes[Au
2Ag
2(C
6F
5)
4(N
![](/images/entities/tbd1.gif)
CCH
3)
2]
n (
1) and [Au
2Cu
2(C
6F
5)
4(N
![](/images/entities/tbd1.gif)
CCH
3)
2]
n (
2) have been carried out. The crystalstructure of both complexes consists of polymeric chains formed by repetition of Au
2Ag
2 or Au
2Cu
2units built up by metallophilic Au(I)···M(I) interactions that are linked through Au(I)···Au(I) interactions.Complexes
1 and
2 are brightly luminescent in the solid state at room temperature and at 77 K withlifetimes in the nanosecond range. Both compounds
1 and
2 undergo oligomerization in solution, asobserved through UV-vis and excitation spectra in acetonitrile solutions at high concentrations. Thus,a correlation between the excitation spectra in solution at different concentrations and the absorptionspectra in the solid state for complex
1 can be established. Time-dependent DFT calculations agree wellwith the experimental results and support the idea of that the origin of the luminescence of these complexesarises from orbitals located in the tetranuclear Au
2M
2 units.