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.