1,3,5-Trithian Mediated Formation of Two New Tetranuclear Silver-Alkynyl Clusters and Investigation of Their Optical Features

For investigating the regulatory effects of the 1,3,5-trithiane (3S) in the formation of silver-alkynyl clusters, two new tetra-nucleus silver-alkynyl clusters, namely, [(3S)4Ag4(PhC≡C)(OTf)2]·OTf·CH3OH (1, OTf = CF3SO3−), and [(3S)2Ag4(tBuC≡C)(tfa)3]n (2, tfa = CF3CO2−), were synthesized and their unique structures were investigated by single-crystal X-ray diffraction, Fourier-transform infrared spectroscopy, and powder X-ray diffraction analysis. Cluster 1 was a discrete cationic tetra-nucleus cluster co-ligated by 3S and phenylacetylene. Cluster 2 was a 2D coordination polymer based on a structurally similar tetra-nucleus cluster linking by 3S. Both clusters show excellent thermal stability and bright solid-state photoluminescence properties at room temperature. This work opens the door to using the supramolecular ligand-thiocrown ether to synthesize Ag clusters of attractive properties.