title: Heterometallic gold(I)-thallium(I) compounds with crown thioethers.
abstract: The polymeric Au/Tl compounds [{Au(C6X5)2}Tl]n (X = Cl, F) react with the crown thioethers 1,4,7-trithiacyclononane ([9]aneS3), 1,5,8,11-tetrathiacyclotetradecane ([14]aneS4), and 1,4,7,10,13,16,19,22-octathiacyclotetracosane ([24]aneS8) in an appropriate molar ratio to afford [{Au(C6X5)2}Tl(L)]2 [L = [9]aneS3, X = Cl (1), F (4); L = [14]aneS4, X = Cl (2), F (5)], [{Au(C6Cl5)2}2Tl2([24]aneS8)]n (3) or [{Au(C6F5)2}2Tl2([24]aneS8)] (6). X-ray diffraction studies of 3, 4 and 6 reveal polymeric (3) or tetranuclear (4, 6) structures formed via Tl-S bonds and AuTl or AuTl and AuAu contacts. All the complexes are luminescent in the solid state, but not in solution, where the metal-metal interactions, which are responsible for the luminescence, are no longer present. DFT calculations on representative model systems of complexes 3, 4 and 6 have also been carried out in order to determine the origin of the electronic transitions responsible for their optical properties.
authors.affiliation: School of Chemistry, The University of Nottingham, University Park, Nottingham, UK.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Rocío
authors.initials: R
authors.lastname: Donamaría
authors.forename: Eduardo J
authors.initials: EJ
authors.lastname: Fernández
authors.forename: Tania
authors.initials: T
authors.lastname: Lasanta
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