A new synthetic methodology has been developed for the preparation of heterobimetallic group 11 and group 12 complexes of a symmetrical bis-NHC "pincer" ligand. The synthetic route involved the initial preparation of a mononuclear [Au(NHC)(2)](+) complex with pendent imidazole moieties on the NHC ligands. Subsequent alkylation of the imidazole groups with Et3OBF4 and metalation with a second metal ion (Ag(I) or Hg(II)) provided two heterobimetallic complexes. Four homobimetallic (Cu(I)(2), Ag(I)(2), Au(I)(2), and Hg(II)(2)) complexes of the same his-NHC "pincer" ligand were also prepared. The homobimetallic Cu(I)(2), Au(I)(2), and Hg(II)(2) complexes and heterobimetallic Au(I)-Ag(I) and Au(I)-Hg(II) complexes and the synthetic intermediates for the heterobimetallic complexes were characterized by X-ray crystallography. These X-ray structures show that the bimetallic complexes adopt "twisted" conformations in the solid state, supporting short M center dot center dot center dot M interactions. Crystalline samples of the homobimetallic Ag(I)(2) and Au(I)(2) and heterobimetallic Au(I)-Ag(I) and Au(I)-Hg(II) complexes were emissive at room temperature and at 77 K. The geometries of the synthesized complexes were optimized at the M06-L/def2-SVP level of theory, and the electronic nature of the M center dot center dot center dot M interactions for all synthesized complexes was investigated using natural bond orbital (NBO) calculations.