Evolution of the Electronic Structure of the trans -[Re 6 S 8 bipy 4 Cl 2 ] Octahedral Rhenium Cluster during Reduction.

Understanding the processes that occur during the redox transformations of complexes coordinated by redox-active apical ligands is important for the design of electrochemically active compounds with functional properties. In this work, a detailed analysis of the interaction energy and electronic structure was performed for cluster complexes trans -[Re 6 S 8 bipy 4 Cl 2 ] n (n = 2-, 4-, 6-, 8-), which can be obtained by stepwise electrochemical reduction of a neutral cluster trans -[Re 6 S 8 bipy 4 Cl 2 ] in DMSO solution. It was shown that the formation of open-shell paramagnetic ions with S = 1, 2 and 1 is the most energetically favorable for n = 2-, 4- and 6-, respectively.