Influence of crown thioether ligands in the structures and of perhalophenyl groups in the optical properties of complexes with argentoaurophilic interactions

  1. Blake, A.J. 3
  2. Donamaria, R. 1
  3. Lippolis, V. 2
  4. López-De-Luzuriaga, J.M. 1
  5. Manso, E. 1
  6. Monge, M. 1
  7. Olmos, M.E. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 University of Cagliari
    info

    University of Cagliari

    Cagliari, Italia

    ROR https://ror.org/003109y17

  3. 3 University of Nottingham
    info

    University of Nottingham

    Nottingham, Reino Unido

    ROR https://ror.org/01ee9ar58

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Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2014

Volumen: 53

Número: 19

Páginas: 10471-10484

Tipo: Artículo

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DOI: 10.1021/IC501515C SCOPUS: 2-s2.0-84907833619 WoS: WOS:000342856800060 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

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Resumen

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 AuI/AgI 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.