Luminescent Copper(I) Halide Adducts of [Au(im(CH(2)py)(2))(2)]PF6 Exhibiting Short Au(I)center dot center dot center dot Cu(I) Separations and Unusual Semibridging NHC Ligands

作者：Strasser Christoph E; Catalano Vincent J^*

来源：Inorganic Chemistry, 2011, 50(21): 11228-11234.

DOI：10.1021/ic201795b

The picolyl-substituted NHC complex [Au(im(CH(2)py)(2))(2)]PF6 (1) reacts with two equivalents of copper(I) halides, affording compounds [Au(im(CH(2)py)(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(CH(2)py)(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)-Cu(I) separations measure 2.7030(5), 2.6688(9), and 2.6786(10) angstrom for 2-4, respectively. Additionally, each Cu(I) center is further coordinated by a semibridging NHC ligand with short Cu-C separations of similar to 2.3 angstrom. In solution, these complexes dissociate the Cu(I) ion. In the solid state, 2-4 are photoluminescent with respective emission maxima of 512, 502, and 507 nm. The reaction of [Au(im(CH(2)py(2))(2)]PF6 with four equivalents of CuBr afforded the coordination polymer {[AuCu2Br2(im(CH(2)py)(2))(2)]Br center dot 3CH(3)CN}(n) (5). This polymeric complex contains [Au(NHC)(2)](+) units interconnected by Cu2Br2 dimers. In 5, the Au-Cu separations are long at 4.23 and 4.79 angstrom, while the Cu-Cu distance is considerably shorter at 2.9248(14) angstrom. In the solid state, 5 is photoluminescent with a broad band appearing at 533 nm.

• 出版日期2011-11-7