X-ray crystallography shows the gold atoms in [R3PAu{SC(OMe)=NC6H4NO2-4}](R = Et, Cy, Ph; 1-3, respectively) and [(Ph2P-R-PPh2){AuSC(OMe)=dNC(6)H(4)NO(2)-4}(2)] (R = CH2, (CH2)(2), (CH2)(3), (CH2)(4), Fc; 4-8, respectively) are linearly coordinated by phosphorus and thiolate-sulfur; weak intramolecular Au center dot center dot center dot O interactions are featured in all structures. The smaller ethyl substituents in 1 allow for supramolecular association via Au center dot center dot center dot S and Au center dot center dot center dot Au interactions that are not found in 2 and 3, which contain larger phosphorus-bound Cy and Ph groups, respectively. Intramolecular Au center dot center dot center dot Au interactions are found in the dppm, dppe, dppp, and Fc structures but not in the dppp analogue, for which an anti conformation was found. The structures have been correlated with the results from photophysical study conducted in the solid state. Thus, photoexcitation of 1-7 with lambda > 350 in the solid state and in solution produces green and blue luminescence, respectively. The spectra in each medium are remarkably similar to each other, and so the emission energy and excitation maxima observed for 1-7 appear to be independent of the nature of the ancillary phosphines, as well as the presence or absence of Au center dot center dot center dot Au interactions, either intermolecularly or intramolecularly.