Effect of Apical Ligands, Substituents and Oxidation States on the Electronic Structure of Co(III) Corrolates

15 September 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Cobalt(III) corroles are the most commonly studied types of metallocorroles, yet the details of their electronic structure, ground spin states and place of redox events are not always straightforward. Corroles are redox active, potentially non-innocent ligands, and it has been found through various experimental and computational techniques, that the innocent or non-innocent behavior is modulated by the apical ligands bound to the cobalt center. In this work, we aim to analyze the effect of corrole substituents and number and type of apical ligands on the electronic structure of cobalt corroles through density functional and wavefunction theories, and to determine the relative energies between closed- and open-shell states. We further perform preliminary analyses on the place of electron abstraction upon oxidation and on the effect of the corrole and apical ligands on the cobalt ligand field splittings. We find that both ligand field and electron-donating or withdrawing effects determine the relative energies of open-shell and closed shell singlet states

Keywords

COBALT
CORROLE
DENSITY FUNCTIONAL THEORY
NON-INNOCENT LIGAND
CASSCF

Supplementary materials

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Supporting Information File
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Supplementary material for article: Effect of Apical Ligands, Substituents and Oxidation States on the Electronic Structure of Co(III) Corrolates. Contains graphs of active space orbitals, tables with results from calculations and coordinates for all optimized geometries
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