AbstractThe reactions of the tetraphosphane donor ligand (Ph2PCH2)2NCH2CH2N(CH2PPh2)2 with the gold precursors [AuCl(tht)] or [Au(C6F5)(tht)] (tht = tetrahydrothiophene) leads to complexes [Au4R4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}] [R = Cl (1) or C6F5 (2)]. Further substitution of the chlorine atoms in 1 by the corresponding 4‐substituted benzenethiolates gives rise to the tetranuclear (phosphane)(thiolato)gold(I) complexes [Au4(S‐C6H4‐X)4{(Ph2PCH2)2NCH2CH2N(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···Au interactions in the case of complex 4. Complexes 3–6 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)