Tetranuclear (Phosphane)(thiolato)gold(I) complexes:: Synthesis, characterization and photoluminescent propertiese

The reactions of the tetraphosphane donor ligand (Ph2PCH2)(2)NCH2CH,N(CH2PPh2)2 with the gold precursors [AuCl(tht)] or (Au(C6F5)(tht)] (tht = tetrahydrothiophene) leads to complexes [Au4R4{(Ph2PCH2)(2)NCH2CH2N(CH2PPh2)(2)}] [R = Cl (1) or C6F5 (2)]. Further substitution of the chlorine atoms in I by the corresponding 4-substituted benzenethiolates gives rise to the tetranuclear (phosphane) (thiolato) gold (I) complexes [Au-4(S-C6H4-X)(4){(Ph2PCH2)(2)NCH2CH2N(CH2PPh2)(2)}] [X = F (3), MeO (4), Me (5) and NO2 (6)]. Complexes 2 and 4 were characterized by X-ray diffraction studies showing Au center dot center dot center dot. An interactions in the case of complex 4. Complexes 36 display intense emissions in the solid state at 77 K with lifetimes in the microsecond range. The observed phosphorescent emissions are attributed to metal-to-ligand charge transfer transitions. Nevertheless, the influence in the emission energies of gold-gold interactions or the contribution of the substituent in the 4-position of the benzenethiolate ring to the excited state cannot be neglected.