The reaction of the tris-indole InTREN ligand (L) with different gold phosphine fragments allows the construction of new gold(l) complexes with different geometries depending on the chosen phosphine. A metallodendrimeric structure is obtained when the gold atom is. linked to a triphenylphosphine ligand, and neutral gold(I) metallocryptands are constructed when a triphosphine is used. Characterization of the compounds was accomplished by P-31{H-1} and H-1 NMR, IR, absorption, and fluorescence spectroscopies, electrospray ionization mass spectrometry (ESI-MS(+)), and elemental analysis, and their geometry was optimized using density functional theory (B3LYP). Time-dependent density functional theory (TD-DFT) calculations have been used to assign the lowest energy absorption bands to LMCT N(p, tertiary amine) -> Au transitions. Photophysical characterization of the complexes shows strong luminescence in the solid state. The formation of heterobimetallic species has been detected in solution in the presence of equimolar quantities of metal cations, and their structures have been identified by a combination of spectroscopic methods and mass spectrometry.