Isolation and Structural X‐ray Investigation of Perfluoroalkyl Derivatives of Six Cage Isomers of C 84

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.