Predicting Bond-Currents in Polybenzenoid Hydrocarbons with an Additivity Scheme

Abstract

We report on the construction and application of a new bond-current additivity scheme for polybenzenoid hydrocarbons. The method is based on identification of the smaller substructures contained in the system, up to tricyclic subunits. Thus, it enables the prediction of any cata-condensed unbranched polybenzenoid hydrocarbon, using a library consisting of only four building blocks. The predicted bond-currents can then be used to generate Nucleus Independent Chemical Shift (NICS) values, the results of which validate previous observations of additivity with NICS-XY-Scans. The limitations of the method are probed, leading to clearly delineated and apparently constant error boundaries, which are independent of the molecular size. It is shown that there is a relationship between the accuracy of the predictions and the molecular structure and specific motifs that are especially challenging are identified. The results of the additivity method, combined with the transparent description of its strengths and weaknesses, ensure that this method can be used with well-defined reliability for characterization of polybenzenoid hydrocarbons. The resource-efficient and rapid nature of the method makes it a promising tool for screening and molecular design.