title: Experimental and Theoretical Reduction Potentials of Some Biologically Active ortho-Carbonyl para-Quinones.
abstract: The rational design of quinones with specific redox properties is an issue of great interest because of their applications in pharmaceutical and material sciences. In this work, the electrochemical behavior of a series of fourp-quinones was studied experimentally and theoretically. The first and second one-electron reduction potentials of the quinones were determined using cyclic voltammetry and correlated with those calculated by density functional theory (DFT) using three different functionals, BHandHLYP, M06-2x and PBE0. The differences among the experimental reduction potentials were explained in terms of structural effects on the stabilities of the formed species. DFT calculations accurately reproduced the first one-electron experimental reduction potentials withR² higher than 0.94. The BHandHLYP functional presented the best fit to the experimental values (R² = 0.957), followed by M06-2x (R² = 0.947) and PBE0 (R² = 0.942).
authors.affiliation: Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, Ignacio Valdivieso 2409, Casilla 9845, Santiago 8940577, Chile. mmartinez@utem.cl.
authors.forename: Maximiliano
authors.initials: M
authors.lastname: Martínez-Cifuentes
authors.affiliation: Laboratorio de Electroquímica del Medio Ambiente, LEQMA, Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile, USACh, Casilla 40, Correo 33, Santiago 9170022, Chile. ricardo.salazar@usach.cl.
authors.forename: Ricardo
authors.initials: R
authors.lastname: Salazar
authors.affiliation: Departamento de Química, Instituto de Ciencias Básicas, Universidad Técnica de Manabí, Av. Urbina y Che Guevara, Portoviejo 130104, Ecuador. oramirez@ciq.uchile.cl.|Campus Río Simpson, Universidad de Aysén, Obispo Vielmo 62, Coyhaique 5952039, Chile. oramirez@ciq.uchile.cl.
authors.forename: Oney
authors.initials: O
authors.lastname: Ramírez-Rodríguez
authors.affiliation: Departamento de Química, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Casilla 653, Santiago 7800003, Chile. bweiss@uchile.cl.
authors.forename: Boris
authors.initials: B
authors.lastname: Weiss-López
authors.affiliation: Instituto de Química de Recursos Naturales, Universidad de Talca, Av. Lircay s/n, Casilla 747, Talca 3460000, Chile. raraya@utalca.cl.
authors.forename: Ramiro
authors.initials: R
authors.lastname: Araya-Maturana
mesh_terms: D000465:Algorithms; D004583:Electrons; D008956:Models, Chemical; D010084:Oxidation-Reduction; D011809:Quinones / Q000737:chemistry*
chemical_list: D011809:Quinones
keywords: cyclic voltammetry; density functional theory; quinones; redox potential; semiquinone