It has been found that several trinuclear complexes of Au-I interact with silver and thallium salts to intercalate Ag+ and Tl+ cations, thereby forming chains. The resulting sandwich clusters center the cations between the planar trinuclear moieties producing structures in which six Au-I atoms interact with each cation in a distorted trigonal prismatic coordination. The resultant (B(3)AB(3)B(3)AB(3))(infinity) pattern of metal atoms also shows short (similar to 3.0 A) aurophilic interactions between BAB molecular centers. These compounds display a strong visible luminescence, under UV excitation, which is sensitive to temperature and the metal ion interacting with the gold. X-ray crystal structures are reported for Ag([Au(mu-C-2,N-3-bzim)](3))(2)BF4. CH2Cl2 (P (1) over bar, Z = 2, a = 14.4505(1)Angstrom; b = 15.098(2)Angstrom; c = 15.957(1)Angstrom; alpha = 106.189(3)degrees; beta = 103.551(5)degrees; gamma = 101.310(5)degrees); Tl([Au(mu-C-2,N-3-bzim)](3))(2)PF6. 0.5C(4)H(8)O (P (1) over bar, Z = 2, a = 15.2093(1)Angstrom; b =15.3931(4)Angstrom; c = 16.1599(4)Angstrom; alpha = 106.018(1)degrees; beta = 101.585(2)degrees; gamma=102.068(2)degrees); and Tl([Au(mu-C(OEt)=NC6H4CH3)](3))(2)PF6. C4H8O (P2(1)/n, Z = 4, a = 16.4136(3)Angstrom; b = 27.6277(4)Angstrom; c = 16.7182(1)Angstrom; beta = 105.644(1)degrees). Each compound shows that the intercalated cation, Ag+ or Tl+, coordinates to a distorted trigonal prism of six Au-I atoms. The counteranions reside well apart from the cations between the cluster chains.