Redox behaviour of [Ru(β-diketonato)3] compounds

The reduction potentials of the Ru-III/II and the Ru-III/IV redox couples of fourteen [Ru(beta-diketonato)(3)] compounds are related both to electronic descriptors that describe the electron donating or withdrawing properties of the R and R' groups on the beta-diketonato ligand (RCOCHCOR')(-), as well as to their density functional theory (DFT) calculated energies. Most of these linear relationships have a R-2 value of above 0.90. The relationship between the experimental reduction potential of both the Ru-III/II and the Ru-IV/III redox couples and their calculated HOMO and LUMO energy values respectively, the latter directly obtainable from the DFT computed output files, can conveniently be used to theoretically predict the redox potentials of related customized [Ru(beta-diketonato)(3)] compounds, prior to synthesis of such compounds. (C) 2020 Elsevier Ltd. All rights reserved.