Very short metallophilic interactions induced by three-center-two-electron perhalophenyl ligands in phosphorescent Au-Cu complexes

  1. López-De-Luzuriaga, J.M. 1
  2. Monge, M. 1
  3. Olmos, M.E. 1
  4. Pascual, D. 1
  5. Rodríguez-Castillo, M. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Revue:
Organometallics

ISSN: 0276-7333

Année de publication: 2012

Volumen: 31

Número: 9

Pages: 3720-3729

Type: Article

DOI: 10.1021/OM300204X SCOPUS: 2-s2.0-84861176266 WoS: WOS:000303954100029 GOOGLE SCHOLAR

D'autres publications dans: Organometallics

Objectifs de Développement Durable

Résumé

The synthesis, structural characterization, and study of the photoluminescent properties of the complexes [Au 3Cu(C 6F 5) 4(N≡CCH=CHPh) 3] n (1) and [Au 2Cu(C 6Cl 5) 3(N≡CCH=CHPh) 2] (2) have been carried out. The crystal structures of complexes 1 and 2 display a common [Au 2Cu(C 6X 5) 2(μ-C 6X 5)(NCCHCHPh) 2] fragment built up through a trinuclear Au 2Cu unit with a perhalophenyl group acting as a three-center-two-electron bridging ligand. In the case of 1 an additional [Au(C 6F 5)(NCCHCHPh)] unit is also present in the asymmetric unit. Both complexes are brightly luminescent in the solid state at room temperature and at 77 K with lifetimes in the nanosecond range for 1 and in the microsecond range for 2. The presence of very short metallophilic interactions seems to be responsible for the low-energy luminescence observed. DFT and time-dependent DFT calculations agree with the experimental results and support the idea of that the origin of the emissions arises from metal-based orbitals and arrive at ligand-based orbitals as charge transfer transitions. © 2012 American Chemical Society.