Blake Alexander J, Donamaría Rocío, Lippolis Vito, López-de-Luzuriaga José M, Manso Elena, Monge Miguel, Olmos M Elena
School of Chemistry, The University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
Inorg Chem. 2014 Oct 6;53(19):10471-84. doi: 10.1021/ic501515c. Epub 2014 Sep 12.
Reaction of [{Au(C6X5)2}Ag]n (X = Cl, F) with the crown thioethers 1,4,7-trithiacyclononane ([9]aneS3), 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4), or 1,4,7,10,13,16,19,22-octathiacyclotetracosane ([24]aneS8) affords a series of heteronuclear Au(I)/Ag(I) compounds of stoichiometry [{Au(C6X5)2}Ag(L)x] (L = [9]aneS3, x = 2 (1, 4); L = [14]aneS4, x = 1 (2, 5); L = [24]aneS8, x = 0.5 (3, 6)) formed via Ag-S bonds and Au···Ag contacts. X-ray diffraction studies of some of these complexes reveal different structural arrangements and nuclearity depending on the nature of the crown thioether ligand and on the presence or absence of aurophilic interactions. All the complexes are luminescent in the solid state but not in solution. Density functional theory calculations on representative model systems of complexes 2-4 and 6 were carried out to determine the origin of the electronic transitions responsible for their optical properties, which strongly depend on the nature of the perhalophenyl groups bonded to gold.
[{Au(C6X5)2}Ag]n（X = Cl，F）与冠醚硫醚1,4,7 - 三硫杂环壬烷（[9]aneS3）、1,4,8,11 - 四硫杂环十四烷（[14]aneS4）或1,4,7,10,13,16,19,22 - 八硫杂环二十四烷（[24]aneS8）反应，得到一系列化学计量比为[{Au(C6X5)2}Ag(L)x]的异核Au(I)/Ag(I)化合物（L = [9]aneS3，x = 2 (1, 4)；L = [14]aneS4，x = 1 (2, 5)；L = [24]aneS8，x = 0.5 (3, 6)），它们通过Ag - S键和Au···Ag接触形成。对其中一些配合物的X射线衍射研究表明，根据冠醚硫醚配体的性质以及亲金相互作用的存在与否，会有不同的结构排列和核数。所有配合物在固态时发光，但在溶液中不发光。对配合物2 - 4和6的代表性模型体系进行了密度泛函理论计算，以确定其光学性质所涉及的电子跃迁的起源，这些光学性质强烈依赖于与金相连的全卤代苯基的性质。
