Abstract
Perfluoroalkylation of a higher fullerene mixture with CF~3~I or C~2~F~5~I, followed by HPLC separation of CF~3~ and C~2~F~5~ derivatives, resulted in the isolation of several C~84~(R^F^)~n~ (n=12, 16) compounds. Single‐crystal X‐ray crystallography with the use of synchrotron radiation allowed structure elucidation of eight C~84~(R^F^)~n~ compounds containing six different C~84~ cages (the number of the C~84~ isomer is given in parentheses): C~84~ (23)(C~2~F~5~)~12~ (I), C~84~ (22)(CF~3~)~16~ (II), C~84~ (22)(C~2~F~5~)~12~ (III), C~84~ (11)(C~2~F~5~)~12~ (IV), C~84~ (16)(C~2~F~5~)~12~ (V), C~84~ (4)(CF~3~)~12~ (VI with toluene and VII with hexane as solvate molecules), and C~84~ (18)(C~2~F~5~)~12~ (VIII). Whereas some connectivity patterns of C~84~ isomers (22, 23, 11) had previously been unambiguously confirmed by different methods, derivatives of C~84~ isomers numbers 4, 16, and 18 have been investigated crystallographically for the first time, thus providing direct proof of the connectivity patterns of rare C~84~ isomers. General aspects of the addition of R^F^ groups to C~84~ cages are discussed in terms of the preferred positions in the pentagons under the formation of chains, pairs, and isolated R^F^ groups.