| Abstract
| - In this paper, density functional theory method is applied to study the dioxygen-binding abilities of transitionmetal macrocyclic complexes and their electrocatalytic activities toward oxygen reduction reaction. Bothend-on and side-on binding modes are examined. Electronic properties, such as ionization potential and Mullikencharge, are evaluated. The effects of central metal, ligand, and substituents on catalyst's dioxygen-bindingability and catalytic activity are investigated. The binding nature of dioxygen adduct is analyzed based onstructure property. The general activity trend observed for phthalocyanines and porphyrins is rationalizedwith the calculated properties. It is illustrated that the catalyst's oxygen reduction activity is related to itsionization potential and dioxygen-binding ability. Cobalt porphyrin derivatives have high ionization potentials,which make them better catalysts than the corresponding iron derivatives, whereas for phthalocyanine systems,iron derivatives have large ionization potential and better dioxygen-binding ability, which make them goodcatalysts.
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