Homopolynuclear TlI and heteropolynuclear AuI-Tl I complexes with organodiselone ligands: Activation of luminescence by intermetallic interactions

  1. Arca, M. 3
  2. Aroz, T. 2
  3. Concepción Gimeno, M. 2
  4. Kulcsar, M. 2
  5. Laguna, A. 2
  6. Lasanta, T. 1
  7. Lippolis, V. 3
  8. López-De-Luzuriaga, J.M. 1
  9. Monge, M. 1
  10. Olmos, M.E. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  3. 3 University of Cagliari
    info

    University of Cagliari

    Cagliari, Italia

    ROR https://ror.org/003109y17

Revista:
European Journal of Inorganic Chemistry

ISSN: 1434-1948

Año de publicación: 2011

Volumen: 14

Número: 14

Páginas: 2288-2297

Tipo: Artículo

DOI: 10.1002/EJIC.201100004 SCOPUS: 2-s2.0-79955597014 WoS: WOS:000290233400012 GOOGLE SCHOLAR lock_openAcceso abierto editor

Otras publicaciones en: European Journal of Inorganic Chemistry

Resumen

The organodiselone ligands 1,1-bis(3-methyl-4-imidazolin-2-selone)methane (L1) and 1,2-bis(3-methyl-4-imidazolin-2-selone)ethane (L2) have been used for the synthesis of homopolynuclear Tl I [{Tl(L)}PF 6] n·(mMeCN) n [L = L1, m = 1 (1); L = L2, m = 0 (2)] and discrete heteropolynuclear [Tl{Au(C 6Cl 5) 2}(L)] [L = L1 (3), L2 (4)] complexes. The crystal structures of complexes 1 and 3 have been determined through X-ray diffraction studies. Complex 1 consists of alternating thallium(I) centres and bidentate Se-donor ligands that result in polymeric chains. The crystal structure of 3 is formed by [Tl(L1)] + cations and [Au(C 6Cl 5) 2] - anions joined together by an unsupported Au⋯Tl interaction. Compounds 3 and 4 are luminescent in the solid state at room temperature and at 77 K with lifetimes in the nanosecond range. DFT and time-dependent (TD)-DFT calculations have been carried out on different model systems including the free ligand L1, a representative model of complex 1 and a model system of complex 3. The character of the frontier molecular orbitals and the TD-DFT prediction of the absorption spectra are used to explain the origin of the luminescence of complexes 3 and 4 as an admixture of metal-metal (Au-Tl)-to-ligand charge transfer (MMLCT) and intraligand (IL) transitions as observed experimentally. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.