Luminescent Copper(I) Halide Adducts of [Au(im(CH2py)2)2]PF6 Exhibiting Short Au(I)路路路Cu(I) Separations and Unusual Semibridging NHC Ligands
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- 作者：Christoph E. Strasser ; Vincent J. Catalano
- 刊名：Inorganic Chemistry
- 出版年：2011
- 出版时间：November 7, 2011
- 年：2011
- 卷：50
- 期：21
- 页码：11228-11234
- 全文大小：888K
- 年卷期：v.50,no.21(November 7, 2011)
- ISSN：1520-510X
文摘
The picolyl-substituted NHC complex [Au(im(CH2py)2)2]PF6 (1) reacts with two equivalents of copper(I) halides, affording compounds [Au(im(CH2py)2)2(CuX)2]PF6 (X = Cl, 2; Br, 3; I, 4). Each complex contains a nearly linearly coordinated [Au(NHC)2]+ center where the two picolyl groups on each im(CH2py)2 ligand chelate a single copper atom. The Cu(I) center resides in a distorted tetrahedral environment and is coordinated to two pyridyl groups, a halide ion, and a gold metalloligand. The Au(I)鈥揅u(I) separations measure 2.7030(5), 2.6688(9), and 2.6786(10) 脜 for 2鈥?b>4, respectively. Additionally, each Cu(I) center is further coordinated by a semibridging NHC ligand with short Cu鈥揅 separations of 2.3 脜. In solution, these complexes dissociate the Cu(I) ion. In the solid state, 2鈥?b>4 are photoluminescent with respective emission maxima of 512, 502, and 507 nm. The reaction of [Au(im(CH2py)2)2]PF6 with four equivalents of CuBr afforded the coordination polymer {[AuCu2Br2(im(CH2py)2)2]Br路3CH3CN}n (5). This polymeric complex contains [Au(NHC)2]+ units interconnected by Cu2Br2 dimers. In 5, the Au鈥揅u separations are long at 4.23 and 4.79 脜, while the Cu鈥揅u distance is considerably shorter at 2.9248(14) 脜. In the solid state, 5 is photoluminescent with a broad band appearing at 533 nm.