title: Influence of crown thioether ligands in the structures and of perhalophenyl groups in the optical properties of complexes with argentoaurophilic interactions.
abstract: 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.
authors.affiliation: School of Chemistry, The University of Nottingham , University Park, Nottingham NG7 2RD, U.K.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Rocío
authors.initials: R
authors.lastname: Donamaría
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: José M
authors.initials: JM
authors.lastname: López-de-Luzuriaga
authors.forename: Elena
authors.initials: E
authors.lastname: Manso
authors.forename: Miguel
authors.initials: M
authors.lastname: Monge
authors.forename: M Elena
authors.initials: ME
authors.lastname: Olmos