Two Novel Heterothiometallic Clusters Modified by 1,1′-Bis(diphenylphosphino) ferrocene (dppf) in Quasi-Closed Bridging Mode: Syntheses, Structures and Properties

Two heterothiometallic clusters modified by 1,1′-bis(diphenylphosphino) ferrocene (dppf) ligand [(Ag4Mo2S8)(dppf)2] (1) and [(Ag4Mo2S6O2)(dppf)2] (2) have been synthesized and characterized. X-ray single-crystal studies reveal that the structures of the two clusters are both hexagonal prism-shaped cages, which are modified by dppf ligands in rarely quasi-closed mode. While, the terminal atoms of the hexagonal prism cages are different, S atoms for 1 and O atoms for 2. The discrete clusters of 1 and 2 are connected to form 2-D supramolecular layers through hydrogen bonds C–H···S, C–H···π for 1 and C–H···O for 2. The different supramolecular interactions may be caused by the different terminal atoms, which also result in different fluorescence emissions and oxidation potentials.