Extended characteristic polynomial estimating the electrochemical behaviour of some 4-(azulen-1-yl)-2,6-divinylpyridine derivatives

Abstract

Six derivatives of 4-(azulen-1-yl)-2,6-divinylpyridine were the subject of experimental determination of oxidation and reduction potentials being reported elsewhere. In this paper, a computational study was employed in order to obtain a function of structure for these potentials. The geometry was optimized at three theory levels (MMFF94, B3LYP and M06), and the following analysis was conducted with the separately saved optimum geometry in each instance. Two families of molecular descriptors (FMPI and EChP) were used to derive structure-based descriptors. Simple linear regressions were extracted with the best of descriptors for each family and level of theory for both potentials. The study revealed that the MMFF94 optimum geometries best explained the selected electro­chemical properties. Furthermore, the EChP family of descriptors, much bigger than FMPI (about 64 times), was able to better explain the connection between the structure and the property. Once more, it has been shown that the eigenproblem has deep roots in structural chemistry.