ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Chemical reactivity descriptors evaluation for determining catalytic activity, redox potential, and oxygen binding of metallophthalocyanines

Cristian Linares-Flores, Ramiro Arratia-Pérez, and Desmond MacLeod Carey

Universidad Autónoma de Chile, San Miguel, Chile

E-mail: desmond.macleod@uautonoma.cl

Abstract: In this article, we employed density functional theory calculation methods to determine the relationship between the chemical hardness (η), intermolecular chemical hardness (η_DA), and nucleophilicity (N) chemical reactivity descriptors, as well as the energy of the occupied frontier orbitals (E_a1g), and the electrocatalytic activity of different metallophthalocyanines [MPc’s with M=Cr(II), Mn(II), Fe(II), Co(I), Ni(II), and Cu(II)] for the oxygen reduction reaction. Our results suggest that η_DA, N, and E_a1g are appropriate parameters to estimate the electrocatalytic activity. On the other hand, the type of the metallic center determines the strength of the oxygen-binding energy, where a strong electronic interaction promotes the efficient electro-reduction of the dioxygen molecule, which is observed experimentally as a high catalytic activity.

Keywords: Metallophthalocyanines; Chemical hardness; Intermolecular chemical hardness; Nucleophilicity index

Full paper is available at www.springerlink.com.

DOI: 10.1007/s11696-017-0212-x

Chemical Papers 71 (11) 2185–2194 (2017)