Influence of the Number of Metallophilic Interactions and Structures on the Optical Properties of Heterometallic Au/Ag Complexes with Mixed-Donor Macrocyclic Ligands.

The reactivity of the polymeric gold(I)/silver(I) compound [Au2Ag2(C6F5)4(OEt2)2] n toward the 12-membered mixed-donor macrocyclic ligands 1,7-diaza-4,10-dithiacyclododecane (L1), 1-aza-4,7,10-trithiacyclododecane (L2), N-quinolinylmethyl-1-aza-4,7,10-trithiacyclododecane (L3), and N, N'-bis(quinolinylmethyl)-1,7-diaza-4,10-dithiacyclododecane (L4) was studied. The reactions were carried out using different molar ratios depending on the coordination properties of the ligands, which were modified by changing the donor atoms present in the macrocyclic framework (sulfur or nitrogen) or by linking one or two methylquinoline pendant-arms at the secondary nitrogen atom(s). X-ray diffraction analysis of the new complexes obtained show a nuclearity that increases on increasing the number of donor atoms in the ligands. The rich structural diversity observed determines different optical responses when the complexes are irradiated with UV-vis light in the solid state and in THF solution. The study of the optical properties reveals that in complexes for which the luminescence is due to metal-metal interactions, higher emission wavelengths are observed as the number of these metallophilic contacts increases, while the luminescence of ionic complexes has its origin in the macrocyclic ligands. TD-DFT calculations were carried out to verify the origin of these interesting structural-optical property relationships.