Chlorination of IPR C 100 Fullerene Affords Unconventional C 96 Cl 20 with a Nonclassical Cage Containing Three Heptagons

Chlorination of C 100 fullerene with a mixture of VCl 4 and SbCl 5 afforded C 96 Cl 20 with a strongly unconventional structure. In contrast to the classical fullerenes containing only hexagonal and pentagonal rings, the C 96 cage contains three heptagonal rings and, therefore, should be classified as a fullerene with a nonclassical cage (NCC). There are several types of pentagon fusions in the C 96 cage including pentagon pairs and pentagon triples. The three‐step pathway from isolated‐pentagon‐rule (IPR) C 100 to C 96 (NCC‐3hp) includes two C 2 losses, which create two cage heptagons, and one Stone–Wales rotation under formation of the third heptagon. Structural reconstruction established C 100 isomer no. 18 from 450 topologically possible IPR isomers as the starting C 100 fullerene. Until now, no pristine C 100 isomers have been confirmed based on the experimental results.