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Tuning the Luminescent Properties of a Ag/Au Tetranuclear Complex Featuring Metallophilic Interactions via Solvent-Dependent Structural Isomerization.
Inorganic Chemistry 2016 November 8
In this paper the reaction products of the basic gold(I) species [Au(C6 Cl5 )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(C6 Cl5 )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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