Luminescent Hepta- and Tetradecanuclear Complexes of 5,5‘-Diethynyl-2,2‘-bipyridine Capped with Triangular Trinuclear Cu3/Ag3 Cluster Units

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Abstract
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 CuI 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 CuI14 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 ReIMI6 and tetradecanuclear CuI14 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 CuI14 complexes is ascribed tentatively to originate from both MLCT [d(Re/Cu) → π* (bpy)] and LMCT (acetylide → M3) transitions.

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