Two heterothiometallic clusters modified by 1,1 0 -bis(diphenylphosphino) ferrocene (dppf) ligand [(Ag 4 Mo 2 S 8 )(dppf) 2 ] (1) and [(Ag 4 Mo 2 S 6 O 2 )(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-HÁÁÁS, C-HÁÁÁp for 1 and C-HÁÁÁO for 2. The different supramolecular interactions may be caused by the different terminal atoms, which also result in different fluorescence emissions and oxidation potentials.