Dual modification to stabilize Non-IPR C72 fullerene: A new theoretical strategy

Abstract

The stabilization of non-IPR fullerenes for their isolation and characterization is an area of recent interest. In the present study, we have explored the stabilization techniques of C₇₂ isomers via endo and exo-modifications and finally approached dual modification. A total of four isomers of C₇₂ have been considered in this study; among them, one is IPR derivative (1), and the rest are non-IPR derivatives with one (2) and two (3 and 4) fused pentagon rings. First, we have studied the endohedral modification by encapsulating one and two La atoms in the C₇₂ cavity. Secondly, we have exohedrally modified the C₇₂ isomers via chlorination by adding four and eight chlorides, respectively. Our final approach is to study the dual modification, where we have implemented both endo exo-modifications together. This dual modification can be achieved in two ways: exo followed by endo and endo followed by exo. For each modification, the relative stability of every modified C₇₂ derivative has been checked by calculating the relative energy with respect to the most stable modified analogue. To find out whether these modifications are energetically feasible or not, we have calculated the binding energy of each modified C₇₂ isomer. The binding energy calculation reveals that the encapsulation and exo-modification techniques are good enough to stabilize the non-IPR C₇₂ derivatives. Moreover, the effectiveness of dual modification has also been established from the enhanced binding energy compared to either endo- or exo-modification. We have also studied the NPA charges on the encapsulated La atoms for each endo- and dual-modified C₇₂ derivative. Furthermore, the AIM study has also been perceived to find out the interaction between the La atom and the fullerene cages for both mono- and di-encapsulated fullerene derivatives and also between La-La centres for di-encapsulated derivatives. Overall, the present theoretical study will provide an idea about the stability of the modified C₇₂ derivatives, which will help the experimentalists to design new strategies for synthesizing modified non-IPR fullerene derivatives that have vast applications in the medicinal and industrial fields.

Keywords: DFT; Dual modification; Endohedral; Exohedral; Isomer.