Formation of C_2v-C₇₂(11188)Cl₄: A Particularly Stable Non-IPR Fullerene

Abstract

Halogenation has been one of the most used strategies to explore the reactivity of empty carbon cages. In particular, the higher reactivity of non-IPR fullerenes, i.e., those fullerenes that do not satisfy the isolated pentagon rule (IPR), has been used to functionalize and capture these less stable fullerenes. Here, we have explored the stability of the non-IPR isomer C(11188) with C symmetry, which is topologically linked to the only IPR isomer of C, as well as its reactivity to chlorination. DFT calculations and Car-Parrinello molecular dynamics simulations suggest that chlorination takes places initially in nonspecific sites, once carbon cages are formed. When the temperature in the arc reactor decreases sufficiently, Cl atoms are trapped on the fullerene surface, migrating from not-so-favored positions to reach the most favored sites in the pentalene. We have also discussed why cage C-C(11188) is found to take four chlorines, whereas cage C-C(14049) is observed to capture 10 of them, even though these two fullerenes are closely related by a simple C insertion.

New Insights into Aromaticity through Novel Delta Polynomials and Delta Aromatic Indices

“…In fact, while the weighted delta index of buckminsterfullerene is higher than both C 70 (D 5h ) and C 72 (C 2v ), this trend is not reproduced by any of the other indices shown in Table 9. We note that both C 72 (C 2v ) and C 72 (D 6d ) structures have been found to be stable isomers [82,83]. Moreover, we note that as the weighted delta indices do not vary in large magnitude, and small changes should be considered important as the weighted indices are subtle in their variations.…”