Multiple evidence for gold(I)...silver(I) interactions in solution.
[AuAg3(C6F5)(CF3CO2)3(CH2PPh3)]n (2) was prepared by reaction of [Au(C6F5)(CH2PPh3)] (1) and [Ag(CF3CO2)] (1:3). The crystal structures of complexes 1 and 2 were determined by X-ray diffraction, and the latter shows a polymeric 2D arrangement built by Au...Ag, Ag...Ag, and Ag...O contacts. The metallophilic interactions observed in 2 in the solid state seem to be preserved in concentrated THF solutions, as suggested by EXAFS, pulsed-gradient spin-echo NMR, and photophysical studies, which showed that the structural motif [AuAg3(C6F5)(CF3CO2)3(CH2PPh3)] is maintained under such conditions. Time-dependent DFT calculations agree with the experimental photophysical energies and suggest a metal-to-ligand charge-transfer phosphorescence process. Ab initio calculations give an estimated interaction energy of around 60 kJ mol(-1) for each Au...Ag interaction.
Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC, Complejo Científico-Tecnológico, 26004 Logroño, Spain.
Eduardo J
EJ
Fernández
Christopher
C
Hardacre
Antonio
A
Laguna
M Cristina
MC
Lagunas
José M
JM
López-de-Luzuriaga
Miguel
M
Monge
Manuel
M
Montiel
M Elena
ME
Olmos
Raquel C
RC
Puelles
Eva
E
Sánchez-Forcada