From K(6)[Re(6−x)Mo(x)S(8)(CN)(5)] Solid Solution to Individual Cluster Complexes: Separation and Investigation of [Re(4)Mo(2)S(8)(CN)(6)](n−) and [Re(3)Mo(3)S(8)(CN)(6)](n−) Heterometallic Clusters

A series of new cluster compounds with {Re(4)Mo(2)S(8)} and {Re(3)Mo(3)S(8)} cores has been obtained and investigated. The clusters with different Re/Mo ratios were isolated as individual compounds, which made it possible to study their spectroscopic and electrochemical properties. The geometry of the new clusters was studied using a combination of X-ray diffraction analysis, XAS and quantum chemical DFT calculations. It was shown that the properties of the new clusters, such as the number and position of electrochemical transitions, electronic structure and change in geometry with a change in charge, are similar to the properties of clusters based on the {Re(4)Mo(2)Se(8)} and {Re(3)Mo(3)Se(8)} cores described earlier.