Martínez-Cifuentes Maximiliano, Salazar Ricardo, Ramírez-Rodríguez Oney, Weiss-López Boris, Araya-Maturana Ramiro
Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, Ignacio Valdivieso 2409, Casilla 9845, Santiago 8940577, Chile.
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.
Molecules. 2017 Apr 4;22(4):577. doi: 10.3390/molecules22040577.
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 four -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 with ² higher than 0.94. The BHandHLYP functional presented the best fit to the experimental values (² = 0.957), followed by M06-2x (² = 0.947) and PBE0 (² = 0.942).
由于醌类化合物在制药和材料科学中的应用，具有特定氧化还原性质的醌类化合物的合理设计是一个备受关注的问题。在这项工作中，对一系列四种醌类化合物的电化学行为进行了实验和理论研究。使用循环伏安法测定了醌类化合物的第一和第二单电子还原电位，并将其与使用三种不同泛函（BHandHLYP、M06-2x和PBE0）通过密度泛函理论（DFT）计算得到的结果进行了关联。根据对所形成物种稳定性的结构影响，解释了实验还原电位之间的差异。DFT计算准确地再现了第一单电子实验还原电位，拟合度R²高于0.94。BHandHLYP泛函与实验值的拟合度最佳（R² = 0.957），其次是M06-2x（R² = 0.947）和PBE0（R² = 0.942）。
