mononuclear Au(I) complex, Au(Spy)(PPh(2)py) (1), has been synthesized and characterized structurally. The complex possesses the expected linear coordination geometry with a S-Au-P bond angle of 176.03(6)degrees and no evidence of aurophilic interactions between nearest neighbor Au(I) ions in the solid state. Protonation of the pendant pyridyl groups;of 1 leads to the formation of the II-bonded dimer [(Au(SpyH)(PPh(2)py))(2)](PF6)(2) (2), which has also been structurally characterized. A linear coordination geometry at the Au(I) ions in 2 with a S-An-P bond angle of 173.7(2)degrees is augmented by evidence of a strong aurophilic interaction with a Au . . . Au distance of 2.979(1) Angstrom. The pendant pyridyl groups of 1 have also been used to bind Cu(I) by reactions with [Cu(NCMe)(4)](PF6) and Cu(P(p-tolyl)(3))(2)(NO3) leading to the formation of the heterobimetallic complexes [{AuCu-(mu -Spy)(mu -PPh(2)py)}(2)](PF6)(2) (3),and [AuCu(P(p-tolyl)(3))(2)(mu -Spy)(mu -PPh(2)py)](NO3) (4), respectively. A structure determination df 3 reveals a tetranuclear complex composed of two AuCu(mu -Spy)(mu -PPh(2)py)(+) units held together by bridging thiolate ligands. A strong metal-metal interaction is noted between the two different d(10) ions with nearest Au-Cu distances averaging 2.6395 A. The S-Au-P bond angles in 3 deviate slightly from linearity due to the Au . . . Cu interactions; while the coordination geometries at Cu(I) are distorted tetrahedral consisting of the two pyridyl nitrogen atoms, a bridging thiolate sulfur, and the interacting Au(I) ion. While mononuclear complex 1 is only weakly emissive in the solid state and in fluid solution, complexes 2-4 show stronger photoluminescence in the solid state and rigid media at 77 K, and in fluid solution. The emission maxima for 2-4 in ambient temperature fluid solution are 470, 635, and 510 nm, respectively. A tentative assignment of the emitting state as a S(p pi) --> Au LMCT transition is made on the basis of previous studies of Au(I) thiolate phosphine complexes. Shifts of lambda (em) result-from the influence of H bonding or Cu(I) coordination on the filed thiolate orbital energy, or on the effect of metal-metal interaction on the Au(I) acceptor orbital energy. Crystal data for Au(Spy)(PPh2py) (1): triclinic, space group P (1) over bar (No. 2), with a = 8.3975(4) Angstrom, b = 11.0237(5) Angstrom, c = 12.4105(6) Angstrom, alpha = 98.6740(10)degrees, beta = 105.3540(10)degrees, gamma = 110.9620(10)degrees V = 995.33(8) Angstrom (3), Z = 2, R1 = 3.66% (1 > 2 sigma (I)), wR2 = 9.04% (I > 2 sigma (I)) for 2617 unique reflections. Crystal data for [(Au(SpyH)(PPh(2)py))(2)](PF6)(2) (2): triclinic, space group P (1) over bar (No. 2), with a = 14.0284(3) Angstrom, b = 14.1093(3) Angstrom, c = 15.7027(2) Angstrom, alpha = 97.1870(10)degrees, beta = 96.5310(10)degrees, gamma = 117.1420(10)degrees, V = 2692.21(9) Angstrom (3), Z = 2, RI = 7.72% (1 > 2 sigma (I)), wR2 = 15.34% (1 > 2 sigma (l)) for 5596 unique reflections. Crystal data for [{AuCu(mu -Spy)(mu -PPh(2)py)}(2)](PF6)(2) (3): monoclinic, space,group P2(1)/c (No. 14), with a = 19.6388(6) Angstrom, b = 16.3788(4) Angstrom, c = 17.2294(5) Angstrom, beta = 91.48 degrees, V = 5540.2(3) Angstrom (3), Z = 4, R1 = 3.99% (1 > 2 sigma (I)), wR2 = 8.38% (1 > 2 sigma (l)) for 10597 unique reflections.