Chlorination of Two Isomers of C₈₆ Fullerene: Molecular Structures of C₈₆(16)Cl₁₆, C₈₆(17)Cl₁₈, C₈₆(17)Cl₂₀, and C₈₆(17)Cl₂₂

Abstract

Chlorination of a mixture of C86 isomers no. 16 (Cs ) and no. 17 (C2 ) with VCl4 or a (TiCl4 +Br2 ) mixture afforded crystalline chlorides with 16 to 22 Cl atoms per fullerene cage. Single crystal X-ray diffraction with the use of synchrotron radiation enabled us to determine the chlorination patterns of C86 (16)Cl16 , C86 (17)Cl18 , C86 (17)Cl20 , and C86 (17)Cl22 . At these degrees of chlorination, addition patterns of C86 (16) and C86 (17) chlorides have some features in common, owing to the close similarity in the cage structures of both isomers. The average energy of CCl bonds decreases with increasing number of attached Cl atoms.

Probing the structure of giant fullerenes by high resolution trapped ion mobility spectrometry

“…We note in passing that free energy differences at elevated temperatures have been proposed as more relevant for describing detailed fullerene isomer distributions as generated by arc discharge. 64 For C n (82 r n r 108) several isomers have been isolated from soot extracts for each n. 4,6,[12][13][14][15][16][17][18][19][20][21][22][23][24][25]65 In most cases the lowest energy isomers of these agree within 0.4% with our experimental CCS value. For C 82 , Achiba 4 identified two isomers, C 82 (7) with C 3v symmetry and C 82 (9) with C 2v symmetry.…”

“…In the size range below C 110 , a large number of isomers has been structurally characterized in condensed phase by different methods such as NMR and X-ray diffraction -without (below C 98 ) or with (above C 88 ) functionalization. [4][5][6][7][12][13][14][15][16][17][18][19][20][21][22][23][24][25] With the DFT and trajectory method procedure outlined above (method 4), we calculated the CCS values for the geometry optimized charged fullerene structures corresponding to those isomeric carbon cage connectivities which have been observed in condensed phase and compared them with the experimental CCS values, see Table 3 and Fig. 4.…”

“…This method has proven to be quite powerful and it has been possible to identify and structurally characterize specific IPR isomers for a large number of fullerene cage sizes ranging up to C 108 . [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] A drawback is however that such giant fullerene isomers can only be identified if they are functionalized in a well-defined way and if the corresponding derivatives can be crystallized. Furthermore, the reaction conditions for fullerene derivatization are often quite harsh and may be associated with isomerization and/or fragmentation.…”

Five Isolated Pentagon Rule Isomers of Higher Fullerene C94 Captured as Chlorides and CF3 Derivatives: C94(34)Cl14, C94(61)Cl20, C94(133)Cl22, C94(42)(CF3)16, and C94(43)(CF3)18

“…In fact, two very similar molecules, C 94 (133)Cl 20 and C 94 (133)Cl 22 , overlap in the same crystallographic site, thus resulting in an averaged composition of C 94 Cl 21.67 . Such a kind of cocrysallization typical for polychloro derivatives of higher fullerenes has also been observed in the crystal structures of C 76 Cl 24–34 and C 86 Cl 18–22 …”

Chlorination‐Promoted Skeletal‐Cage Transformations of C88 Fullerene by C2 Losses and a CC Bond Rotation

“…6b However, the whole scheme of the branched cage transformation of C 88 (33) presented in Figure 2 is an exceptional case in which all transformation steps are experimentally determined unambiguously rather than deduced by a reconstruction of the pathway. Recently, another case of a branched skeletal transformation of C 86 (16) was reported that consisted, however, from two interchangeable C2Ls and the same final chloride of C 82 ( NC 2) 6d…”