Perhalophenyl(tetrahydrothiophene)gold(I) complexes as lewis bases in acid-base reactions with silver trifluoroacetate

Reaction of [Ag(CF3CO2)] with [Au(C6X5)(tht)] (X = halogen, tht = tetrahydrothiophene) leads to the synthesis of complexes [AgAu(C6F5)(CF3CO2)(tht)](n) (1), [Ag2Au(C6Cl2F3)(CF3CO2)(2)(tht)](n) (2), or [AgAu(C6Cl5)(CF3CO2)(tht)](n) (3), confirming the capability of a neutral complex, such as a perhalophenyl(tetrahydrothiophene)gold(I), to act as electron density donor when treated with a Lewis acid substrate. All three crystal structures have been established by X-ray diffraction; all display (AuAg)-Ag-center dot center dot center dot and (AgAg)-Ag-center dot center dot center dot interactions and polymeric ID (2, 3) or 2D (1) networks built by means of additional (AuAu)-Au-center dot center dot center dot, (Ag-OAg)-Ag-center dot center dot center dot, or Au-(SAg)-Ag-center dot center dot center dot interactions. Complexes 1-3 are luminescent in the solid state at room temperature, and at 77 K Or in frozen solutions they show a different luminescence in the solid state, which seems to be related to the different number and types of metal-metal interactions present in each case. DFT and TDDFT calculations on simplified model systems of 1-3 have also been carried out.