Comparing Isoelectronic, Quadruple-Bonded Metalloporphyrin and Metallocorrole Dimers: Scalar-Relativistic DFT Calculations Predict a >1 eV Range for Ionization Potential and Electron Affinity

[Image: see text] A scalar-relativistic DFT study of isoelectronic, quadruple-bonded Group 6 metalloporphyrins (M = Mo, W) and Group 7 metallocorroles (M = Tc, Re) has uncovered dramatic differences in ionization potential (IP) and electron affinity (EA) among the compounds. Thus, both the IPs and EAs of the corrole derivatives are 1 eV or more higher than those of the porphyrin derivatives. These differences largely reflect the much lower orbital energies of the δ- and δ*-orbitals of the corrole dimers relative to those of the porphyrin dimers, which in turn reflect the higher (+III as opposed to +II) oxidation states of the metals in the former compounds. Significant differences have also been determined between Mo and W porphyrin dimers and between Tc and Re corrole dimers. These differences are thought to largely reflect greater relativistic destabilization of the 5d orbitals of W and Re relative to the 4d orbitals of Mo and Tc. The calculated differences in IP and EA should translate to major differences in electrochemical redox potentials—a prediction that in our opinion is well worth confirming.