Luminescent Hepta- and Tetradecanuclear Complexes of 5,5'-Diethynyl-2,2'-bipyridine Capped with Triangular Trinuclear Cu3/Ag3 Cluster Units
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- 作者：Qiao-Hua Wei ; Gang-Qiang Yin ; Li-Yi Zhang ; Zhong-Ning Chen
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：December 11, 2006
- 年：2006
- 卷：45
- 期：25
- 页码：10371 - 10377
- 全文大小：133K
- 年卷期：v.45,no.25(December 11, 2006)
- ISSN：1520-510X
文摘
Heteroheptanuclear ReM6 (M = Cu 2, Ag 3) complexes of 5,5-diethynyl-2,2'-bipyridine were prepared by thereaction of [M2(
-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) with the precursor compound Re(Me3SiC
CbpyCCSiMe3)(CO)3Cl in the presence of potassium fluoride by fluoride-catalyzed desilylation. When[Cu2(-dppm)2(MeCN)2]2+ reacts directly with Me3SiCCbpyCCSiMe3, a binuclear CuI complex [Cu2(-dppm)2(SiMe3CCbpyCCSiMe3)2]2+ (4) was isolated. Further addition of [Cu2(-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(-dppm)14(CCbpyCC)2]10+, which is composed of a binuclear Cu2(-dppm)2 and four triangular trinuclearCu3 units. Both heteroheptanuclear ReIMI6 and tetradecanuclear CuI14 complexes display luminescence in bothsolid 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) 
* (bpy)] and LMCT (acetylide M3) transitions.
-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) with the precursor compound Re(Me3SiCCbpyCCSiMe3)(CO)3Cl in the presence of potassium fluoride by fluoride-catalyzed desilylation. When[Cu2(-dppm)2(MeCN)2]2+ reacts directly with Me3SiCCbpyCCSiMe3, a binuclear CuI complex [Cu2(-dppm)2(SiMe3CCbpyCCSiMe3)2]2+ (4) was isolated. Further addition of [Cu2(-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(-dppm)14(CCbpyCC)2]10+, which is composed of a binuclear Cu2(-dppm)2 and four triangular trinuclearCu3 units. Both heteroheptanuclear ReIMI6 and tetradecanuclear CuI14 complexes display luminescence in bothsolid 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) * (bpy)] and LMCT (acetylide M3) transitions.