Two luminescent triangle and square complexes with the general formulas [ClRe(CO)(3)(mu-DPB)](4) (1) and [BrRe(CO)(3)(mu-BPDB)](3) (2), where DPB = 4,4'-dipyridylbutadiyne and BPDB = 1,4-bis(4'-pyridylethynyl)-2,5-dihexyloxybenzene, were prepared by self-assembly reactions of XRe(CO)(5) (X = Cl or Br) and the corresponding bis-monodentate ligands. The structures of these molecules were confirmed by a variety of techniques including NMR spectroscopy, IR spectroscopy, FAB(+) mass spectrometry, and elemental analysis.