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Tuning the Luminescent Properties of a Ag/Au Tetranuclear Complex Featuring Metallophilic Interactions via
Rocío Donamaría1, M Concepción Gimeno2, Vito Lippolis3
1Departamento de Química, Universidad de La Rioja. Centro de Investigación de Síntesis Química. Complejo Científico-Tecnológico , 26004 Logroño, Spain.
Abstract:
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.
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