Abstract
A new pyrazole ligand with flexible thioether chelate arms was synthesized and was used to obtain an unprecedented class of hexanuclear coinage metal complexes of general formula [MM'L]3Y3 (M, M' = Cu, Ag, Au; Y = OTf, BF4). Three of them were characterized by X-ray crystallography, namely, homometallic [Ag2L]3(OTf)3 and [Ag2L]3(BF4)3 as well as heterometallic [CuAgL]3(OTf)3, revealing that the classical [M(μ-pz)]3 core is crowned by a second deck of S-bound M' ions. Depending on the solvent, these oligonuclear systems undergo rapid dynamics and show cation-anion aggregation in solution, which has been investigated by DOSY and temperature dependent NMR spectroscopy. Preliminary luminescence data for selected hexametallic [MM'L]3Y3 complexes show that the combination of ligand-directed intramolecular and supramolecular d(10) metal ion interactions in the solid state gives rise to synergic emissive properties that allow for a selective addressing of different emission wavelengths.
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