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

ABSTRACT: 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

SUBMITTER: Conradie J 

PROVIDER: S-EPMC9955219 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature