Modulating stability of functionalized fullerene cations [R-C ] with the nature of R-group.

In this study, the first comprehensive theoretical investigation of the stability of functionalized fullerene-based cations [R-C ] and its relationship with the nature of the attached R-group was performed. C -Fullerene core was functionalized with an alkyl group of different length (R = (CH ) CH , where n = 0-9). This set was further complemented by bulky isopropyl and tert-butyl and conjugated phenyl groups. A detailed study of the relative stability of target cationic species was accompanied by in-depth investigation of their electronic structure and aromaticity using a large set of descriptors of different nature. The stability of target species was considered with respect to two alternative and competing mechanisms of bond breaking, namely, heterolytic ([R-C ] → R + C ) and homolytic ([R-C ] → R + C ) ones. The transformation of strained sp -carbon atom in unperturbed C -fullerene to nonconstrained tetrahedral sp -type in functionalized derivatives was found to be the driving force for the formation of its functionalized cations. In spite of the fact that all systems under consideration were found to be corresponding to local minima on corresponding potential energy surfaces, the functionalization of C -core with the smallest and simplest methyl group resulted in most stable compound, as evaluated by bonding energy between R and fullerene fragment (in the light of both mechanisms). Subsequent elongation of the alkyl chain or introducing bulky groups led to notable decrease of the bonding energy and, as consequence, of the stability within the framework of heterolytic bond cleavage, whereas homolytic pathway assumes opposite-slight increase of stability along with lengthening of the R-group. The orbital interaction (ΔE ) was identified as the main driving force for these trends. In general, the homolytic path was found to be dominating for small-length R-groups such as those with n = 0 and 1. At n = 2, heterolytic and homolytic pathways are equally probable (the difference in corresponding bonding energies is about 1 kcal/mol). However, when the alkyl chain becomes longer (n = 3-9), the cationic bond cleavage appears as the most energetically favorable. © 2018 Wiley Periodicals, Inc.