Very short metallophilic interactions induced by three-center-two-electron perhalophenyl ligands in phosphorescent Au-Cu complexes
- López-De-Luzuriaga, J.M. 1
- Monge, M. 1
- Olmos, M.E. 1
- Pascual, D. 1
- Rodríguez-Castillo, M. 1
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1
Universidad de La Rioja
info
ISSN: 0276-7333
Any de publicació: 2012
Volum: 31
Número: 9
Pàgines: 3720-3729
Tipus: Article
Altres publicacions en: Organometallics
Objectius de Desenvolupament Sostenible
Resum
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.