New Insights into the Au(I)···Pb(II) Closed-Shell Interaction: Tuning of the Emissive Properties with the Intermetallic Distance

  1. Echeverría, R. 1
  2. López-De-Luzuriaga, J.M. 1
  3. Monge, M. 1
  4. Moreno, Sonia . 1
  5. Olmos, M.E. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2016

Volumen: 55

Número: 20

Páginas: 10523-10534

Tipo: Artículo

DOI: 10.1021/ACS.INORGCHEM.6B01749 SCOPUS: 2-s2.0-84992117865 WoS: WOS:000385785700067 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

Resumen

Reaction of [Au2Ag2R4(Et2O)2] (R = C6Cl2F3 - or C6F5 -) with [Pb{HB(pz)3}]Cl in a 1:2 molar ratio led to complexes [AuPb{HB(pz)3}R2] (R = C6Cl2F3 - (2) or C6F5 - (3)) through transmetalation reactions. The crystal structures of these complexes display unsupported Au(I)···Pb(II) interactions of 3.0954(4) (2) and 3.2778(4) (3) Å, together with one (2) or two (3) F···Pb weak contacts. These intermetallic distances are compared to the shortest one found for the previously reported complex [Pb{HB(pz)3}Au(C6Cl5)2] (1) of 3.0494(4) (1) Å, showing a clear dependence with the donating properties of the different aurate units. The complexes are emissive in the solid state due to charge transfer transitions associated with the presence of Au(I)···Pb(II) interactions, in which the intermetallic distance plays a crucial role. Density functional theory and time-dependent density functional theory calculations support the assignment of the luminescent properties of the complexes. Ab initio Hartree-Fock and MP2 calculations on model systems of complexes 2 and 3 show the presence of strong Au(I)···Pb(II) closed-shell interactions of an ionic plus dispersive nature together with weak F···Pb contacts of a dispersive origin in the case of complexes 2 and 3. © 2016 American Chemical Society.