C60 Framework Response to Halogen Addition: the Stable Isomers of C60Br2m

The isolation and spectroscopic characterization of halogenated fullerene-60 compounds has not advanced greatly during the 2 years of effort in this area. While the fully fluorinated C60F60 has been studied in some detail, other halogen addition processes have indicated chlorination up to C60Cl24 and bromination up to C60Br24. However, definitive structural information has to date only been provided for three compounds, namely C60Br6, C60Br6 and C60Br24. Iodine does not appear to form genuine addition compounds. In the work reported here semiempirical calculations using the AM1 approximation with the MOPAC molecular orbital program have been directed to comparing the possible stable isomers of the 1:1 addition compounds C60X2 for X = F, Cl and Br. The favoured isomers can be described as 1,2-additions (to a double bond at a hexagon-hexagon fusion) and 1,4-additions (to the terminal carbons of a butadiene moiety) with higher-energy isomers resulting from 1,6- and 1,8-additions. The other isomers represented by 1,3- 1,5- and 1,7-additions are only stable relative to dissociation in the case of the fluorine addition compounds. By contrast for Br2 addition only the 1,2- and 1,4-isomers are stable toward dissociation. The calculations show that, at and near the addition site carbons, X2 addition is adequately described in terms of local distortion of the C60 sphere. The elementary model of C60 as comprising formal single and double bonds is relevant since C60 behaves as a 'poly- alkene ', with sp3 carbons replacing sp2 carbons at the addition sites. This model offers an explanation for the unique structures observed for C60Br6 and C60Br24 which the AM1calculations show to be very stable toward dissociation. However, the experimental C60Br8 structure is found to be relatively less stable than another isomer. Also high-stability isomers of C60Br4, C60Br10, C60Br12 and C60Br18 are predicted.