Heteroheptanuclear ReM₆ (M = Cu 2, Ag 3) complexes of 5,5-diethynyl-2,2‘-bipyridine were prepared by the reaction of [M₂(μ-dppm)₂(MeCN)₂]²⁺ (dppm = bis(diphenylphosphino)methane) with the precursor compound Re(Me₃SiC⋮CbpyC⋮CSiMe₃)(CO)₃Cl in the presence of potassium fluoride by fluoride-catalyzed desilylation. When [Cu₂(μ-dppm)₂(MeCN)₂]²⁺ reacts directly with Me₃SiC⋮CbpyC⋮CSiMe₃, a binuclear Cu^I complex [Cu₂(μ-dppm)₂(SiMe₃C⋮CbpyC⋮CSiMe₃)₂]²⁺ (4) was isolated. Further addition of [Cu₂(μ-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^I₁₄ complex [Cu₁₄(μ-dppm)₁₄(C⋮CbpyC⋮C)₂]¹⁰⁺, which is composed of a binuclear Cu₂(μ-dppm)₂ and four triangular trinuclear Cu₃ units. Both heteroheptanuclear Re^IM^I₆ and tetradecanuclear Cu^I₁₄ 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^I₁₄ complexes is ascribed tentatively to originate from both MLCT [d(Re/Cu) → π* (bpy)] and LMCT (acetylide → M₃) transitions.

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