Heteroheptanuclear ReM6 (M = Cu 2, Ag 3) complexes of 5,5-diethynyl-2,2 '-bipyridine were prepared by the reaction of [M-2(mu-dppm)(2)(MeCN)(2)](2+) (dppm = bis(diphenylphosphino)methane) with the precursor compound Re( Me3SiC equivalent to CbpyC equivalent to CSiMe3)(CO)(3)Cl in the presence of potassium fluoride by fluoride-catalyzed desilylation. When [Cu-2(mu-dppm)(2)(MeCN)(2)](2+) reacts directly with Me3SiC equivalent to CbpyC equivalent to CSiMe3, a binuclear Cu-I complex [Cu-2(mu-dppm)(2)( SiMe3C equivalent to CbpyC equivalent to CSiMe3)(2)](2+) (4) was isolated. Further addition of [Cu-2(mu-dppm)(2)(MeCN)(2)](2+) into a THF-MeOH (3:1, v/v) solution of 4 in the presence of potassium fluoride induced isolation of a tetradecanuclear Cu-14(I) complex [Cu-14(mu-dppm)(14)(C equivalent to CbpyC equivalent to C)(2)](10+), which is composed of a binuclear Cu-2(mu-dppm)(2) and four triangular trinuclear Cu-3 units. Both heteroheptanuclear (ReM6I)-M-I and tetradecanuclear Cu-14(I) complexes display luminescence in both solid states and dichloromethane solutions at room temperature with emissive lifetimes in the range of microseconds. The dual emissive feature for the ReM6 and Cu-14(I) complexes is ascribed tentatively to originate from both MLCT [d(Re/Cu) -> pi* (bpy)] and LMCT (acetylide -> M-3) transitions.