Isolation and Structural X‐ray Investigation of Perfluoroalkyl Derivatives of Six Cage Isomers of C84

Perfluoroalkylation of a higher fullerene mixture with CF₃I or C₂F₅I, followed by HPLC separation of CF₃ and C₂F₅ derivatives, resulted in the isolation of several C₈₄(R^F)_n (n=12, 16) compounds. Single‐crystal X‐ray crystallography with the use of synchrotron radiation allowed structure elucidation of eight C₈₄(R^F)_n compounds containing six different C₈₄ cages (the number of the C₈₄ isomer is given in parentheses): C₈₄ (23)(C₂F₅)₁₂ ( I ), C₈₄ (22)(CF₃)₁₆ ( II ), C₈₄ (22)(C₂F₅)₁₂ ( III ), C₈₄ (11)(C₂F₅)₁₂ ( IV ), C₈₄ (16)(C₂F₅)₁₂ ( V ), C₈₄ (4)(CF₃)₁₂ ( VI with toluene and VII with hexane as solvate molecules), and C₈₄ (18)(C₂F₅)₁₂ ( VIII ). Whereas some connectivity patterns of C₈₄ isomers (22, 23, 11) had previously been unambiguously confirmed by different methods, derivatives of C₈₄ isomers numbers 4, 16, and 18 have been investigated crystallographically for the first time, thus providing direct proof of the connectivity patterns of rare C₈₄ isomers. General aspects of the addition of R^F groups to C₈₄ cages are discussed in terms of the preferred positions in the pentagons under the formation of chains, pairs, and isolated R^F groups.