Tuning the Luminescent Properties of a Ag/Au Tetranuclear Complex Featuring Metallophilic Interactions via Solvent-Dependent Structural Isomerization

  1. Donamaría, R. 1
  2. Gimeno, M.C. 2
  3. Lippolis, V. 3
  4. López-De-Luzuriaga, J.M. 1
  5. Monge, M. 1
  6. Olmos, M.E. 1
  1. 1 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Universidad de Zaragoza

    Universidad de Zaragoza

    Zaragoza, España

    ROR https://ror.org/012a91z28

  3. 3 University of Cagliari

    University of Cagliari

    Cagliari, Italia

    ROR https://ror.org/003109y17

Inorganic Chemistry

ISSN: 0020-1669

Year of publication: 2016

Volume: 55

Issue: 21

Pages: 11299-11310

Type: Article

DOI: 10.1021/acs.inorgchem.6b01819 SCOPUS: 2-s2.0-84994589884 WoS: WOS:000387428200052 GOOGLE SCHOLAR


In this paper the reaction products of the basic gold(I) species [Au(C6Cl5)2]- against the acid salt Ag(OClO3) in the presence of the S-donor macrocyclic ligand 1,4,7-trithiacyclononane ([9]aneS3) are studied in different solvents. Two different isomers of stoichiometry [{Au(C6Cl5)2}Ag([9]aneS3)]2 were isolated depending on the solvent used, dichloromethane or tetrahydrofuran, which show different luminescence in the solid state. X-ray diffraction studies of these compounds reveals that both show the same heteropolynuclear Ag···Au···Au···Ag system but with different Au···Au interaction distances and different relative positions of the cationic fragment [Ag([9]aneS3)]+ in the structure with respect the bimetallic Au···Au core. This work includes a study of the optical properties of both isomers, as well as time-dependent density functional theory calculations that were performed to determine the origin of their different luminescence. © 2016 American Chemical Society.