Supplementary Information Two Ih-symmetry-breaking C60 isomers stabilized by

chlorination Yuan-Zhi Tan*, Zhao-Jiang Liao*, Zhuo-Zhen Qian, Rui-Ting Chen, Xin Wu, Hua Liang, Xiao Han, Feng Zhu, Sheng-Jun Zhou, Zhiping Zheng, Xin Lu, Su-Yuan Xie†, Rong-Bin Huang & Lan-Sun Zheng State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China * These authors contributed equally to this work † email: syxie@xmu.edu.cn

Contents

1. The picture summarizing the main results of this paper……....(2)

2. Isolation and analysis………………………………………….(3)

3. Characterization……………………………………………….(5)

4. Relative Energy of C60 isomers and the related chlorinated

derivatives……………………………………………………….(14)

5. The curvature of the C60 cage surfaces………………………..(18)

6. Chemical reactivity and characterization of C60 isomer

derivatives.....................................................................................(18)

7. The MSn and thermal dechlorination results of #1804C60Cl12…...(24)

8. The yield correlation among #1809C60Cl8, Ih-C60 and D5h-C70…..(26)

9. The full list of Refs 13, 19, 21, 25, 26, and 30………………...(27)

10. Supplement references……………………………………….(28)

1

1. The picture summarizing the main results of this paper.

Supplementary Figure 1: A total of 1812 C60 isomers are flying out from the “pandora’s box” in the sequence of stability. Two of higher-energy isomers are captured by chlorines,

then further functionalized regioselectively. Isomerization towards the most stable buckminsterfullerene is demonstrated.

2

2. Isolation and analysis.

The produced compounds, extracted by toluene in a supersonic bath from the

carbonaceous soot, were analyzed by high performance liquid

chromatography-ultraviolet/visible spectroscopy-mass spectrometry

(HPLC-UV/Vis-MS) using an Agilent 1200 series instrument coupled with a Bruker

Esquire HCT mass spectrometer interfaced by atmospheric pressure chemical

ionization (APCI). Fig. S2 shows a HPLC chromatogram acquired on a Discovery

C18 column (4.6 I.D. × 250mm) of SUPELCO and eluted by a gradient

methanol-ethanol-cyclohexane (Table S1) at a flow rate of 0.8 mL/min.

Supplementary Table 1: Gradient methanol-ethanol-cyclohexane procedure for the

HPLC

Time (min) Methanol (vol.%) Ethanol (vol.%) Cyclohexane (vol.%)

0 100 0 0 15 100 0 0 30 85 15 0 60 55 10 35

120 55 10 35

Preparative isolation was conducted on a LC908W-C60 HPLC instrument (Japan

Analytical Industry Co. Ltd.) using a Cosmosil Buckyprep column (10 I.D. × 250 mm)

eluted with toluene at a flow of 1.9 mL/min under 43 oC temperature. The

components with retention time of around 19.5 and 21.1 min were purified through

multistage recyclic HPLC separation to afford pure #1809C60Cl8 (1) and #1804C60Cl12 (2),

respectively.

3

Supplementary Figure 2: HPLC chromatogram (360 nm) of the toluene-soluble crude products

Owing to weight loss after the tedious multistage HPLC isolation, the weight of

isolated pure component is always lower than the amount originally produced in our

carbon arc experiment. Therefore, the yield of the products can not be valuated with

reliability on the basis of the isolated weight. We adopted the HPLC chromatographic

peak area at retention time of 63.5 min (Fig. S2) to valuate the weight content of 1,

based on the linear correlation of the corresponding chromatographic area vs. the

concentration of 1 (Fig. S3). 6.1 mg toluene-soluble components, extracted from 18

mg crude sample produced in the optimal synthesis conditions, were dissolved

into10.0 mL toluene and analyzed by the proposed HPLC method. This solution

displays a symmetric chromatographic peak areas of 2.53 mAU × min at 63.5min for #1809C60Cl8, 46.2 mAU × min at 80.1 min for Ih-#1812C60, and 9.6 mAU × min at 103.3

for D5h-#8149C70 min, that indicate a concentration of 21.3 µg/mL for #1809C60Cl8, 25.4

µg/mL for #1812C60, 16.2 µg/mL for #8149C70, according to the linear correlation plots

(Fig. S3). Therefore, the weight content of 1 in the toluene-extracted crude products is

valuated as ~3.5 %, while the #1812C60 and #8149C70 are 4.2% and 2.6%, respectively.

We fail to quantify the yield of 2 because the HPLC chromatographic signal of 2 in

the crude products is too weak to be adopted for estimation of its yield, but the

isolated weight of 2 is about at a tenth part that of 1. Accordingly, about 300 mg of 1

4

and 30 mg of 2 can be synthesized in a regular arc-discharge set-up[S1] if 25 g soot is

produced each day. To obtain pure samples, however, tedious multistage HPLC

isolations are required.

Supplementary Figure 3: The linear correlation plots of C2v-#1809C60Cl8, Ih-#1812C60, D5h-#8149C70 with the peak areas vs. the concentration

3. Characterization.

3.1. Crystallographic characterization for #1809C60Cl8.

Dark-red crystals of #1809C60Cl8 suitable for X-ray diffraction studies were obtained

by solvent evaporation from its lemon yellow toluene solution.

A block of #1809C60Cl8 crystal with dimensions of 0.48 × 0.40 × 0.24 mm was

selected for X-ray diffraction determination. The diffraction data were collected on a

Bruker Smart Apex-2000 CCD diffractometer using a graphite-monochromated Mo

Kα (λ = 0.71073 Å) radiation with a ω scan mode at 173 K. The crystal belongs to

triclinic system, space group P-1 with the cell parameters: a = 9.786(2), b = 11.733(2),

c = 17.774(3) Å, α = 90.510(3), β = 100.921(3), γ = 104.349(3)º, V = 1938.0(6) Å3, Z

= 2. A total of 14918 reflections were measured in the θ range (1.17 ≤ θ ≤ 26.00º) and

7409 were independent with Rint = 0.0160, of which 7023 were considered as

observed (I > 2σ(I)). Lorentz-polarization and absorption corrections were applied.

The structure was solved by direct methods with SHELXS-97 program and refined by

full-matrix least-squares calculations with SHELXL-97 program based on F2 [S2,S3].

All non-hydrogen atoms were refined anisotropically and the hydrogen atoms were

5

located at the calculated positions. The final full-matrix least-squares refinement gave

R = 0.0370, wR = 0.1096 (w = 1/[σ2(Fo2)+(0.0753 P)2+1.3517P]), where P =

(Fo2+2Fc

2)/3, S = 1.021, (∆/σ)max = 0.001, (∆ ρ)max = 0.417, (∆ ρ)min = -0.303 e/Å3.

CCDC-629002 contains the supplementary crystallographic data of #1809C60Cl8. These

data can be obtained free of charge from the Cambridge Crystallographic Data Centre

via www.ccdc.cam.ac.uk/data_request/cif.

3.2. 13C NMR, IR, UV/Vis and MS data of #1809C60Cl8.

3.2.1. 13C NMR spectrum of #1809C60Cl8.

Supplementary Figure 4: 13C NMR spectrum of #1809C60Cl8, measured in CCl3D

solution. The data (listed in Table S2) were acquired on a Bruker AV 400 instrument of 100.622 MHz after 154,902 scans at 27 oC under 30o exiting pulse with 3 s repetition time.

Supplementary Table 2: The list of the 13C NMR data of #1809C60Cl8.

Number of carbon Chemical shift ( ppm )

1 68.15 2 85.04 3 138.11 4 142.27

6

5 144.97 6 145.40 7 145.69 8 146.48 9 146.96 10 147.31 11 147.53 12 147.85 13 148.54 14 148.80 15 148.99 16 149.38 17 150.64

3.2.2. Mass spectrum of #1809C60Cl8.

Supplementary Figure 5: Mass spectrum of #1809C60Cl8.

7

3.2.3. IR spectrum of #1809C60Cl8.

Supplementary Figure 6: IR spectrum of #1809C60Cl8 recorded on a KBr crystal

disc coated with the #1809C60Cl8 solid film.

3.2.4. UV/Vis spectrum of #1809C60Cl8.

Supplementary Figure 7: UV/Vis spectrum of #1809C60Cl8.

8

3.3. Crystallographic characterization for #1804C60Cl12.

Brown crystals of #1804C60Cl12 suitable for X-ray diffraction studies were obtained by

solvent evaporation from its golden yellow carbon disulfide solution.

A crystal of #1804C60Cl12 with dimensions of 0.04 × 0.03 × 0.02mm was selected for

X-ray diffraction determination. The diffraction data were collected on an Oxford

CCD diffractometer using a graphite-monochromated Cu Kα (λ = 1.54178 Å)

radiation with the ω scan mode at room temperature. The crystal belongs to triclinic

system, space group P-1 with the cell parameters: a = 11.9854(7), b = 12.6847(6), c =

13.8606(8) Å, α = 76.079(4), β = 76.266(5), γ = 77.522(5)°, V = 1958.4 (2) Å3, Z = 2.

A total of 13735 reflections were measured in the θ range (3.35 ≤ θ ≤ 60.84) and 5692

were independent with Rint = 0.0363, of which 3490 were considered as observed (I >

2σ(I)). Lorentz-polarization and absorption correction were applied. The structure was

solved by direct methods with SHELXS-97 program and refined by full-matrix

least-squares calculations with SHELXL-97 program based on F2 [S2,S3]. All atoms

were refined anisotropically. The final full-matrix least-squares refinement gave R =

0.0703, wR = 0.1957 (w = 1/[σ2(F02)+(0.1377P)2+0.0000P]), where P = ( F0

2+2Fc2)/3,

S = 1.038, (∆/α)max = 0.162, (∆ρ)max = 1.479, (∆ρ)min= -0.531 e/Å3. CCDC-678135

contains the supplementary crystallographic data of #1804C60Cl12. These data can be

obtained free of charge from the Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

9

3.4. 13C NMR, IR, UV/Vis and MS data of #1804C60Cl12.

3.4.1. 13C NMR spectrum of #1804C60Cl12.

Supplementary Figure 8: 13C NMR spectrum of #1804C60Cl12 measured in C6D6 solution. The data (listed in Table S3) were acquired on a Bruker AV 600 instrument of 150.862 MHz after 80,121 scans at 20 oC under 30o exiting pulse with 3 s repetition time. The

below spectrum is the amplified plot of the upper one. The peak marked with star (*) is assigned to the 13C NMR signal of toluene.

10

Supplementary Table 3: The list of the 13C NMR data of #1804C60Cl12.

number of carbon chemical shift (ppm)

1 71.86 2 72.62 3 72.82 4 73.27 5 74.71 6 74.95 7 75.41 8 75.91 9 76.96 10 77.38 11 84.00 12 85.00 13 134.34 14 136.55 15 137.22 16 137.30 17 139.17 18 139.81 19 140.06 20 140.30 21 140.90 22 140.98 23 141.01 24 141.32 25 143.71 26 144.17 27 145.29 28 145.38 29 146.15 30 146.86 31 147.30 32 147.45 33 147.55 34 148.01 35 148.19 36 148.28 37 148.64 38 148.67 39 148.73 40 148.75

11

41 148.83 42 148.91 43 149.16 44 149.28 45 149.38 46 149.49 47 149.60 48 149.68 49 150.25 50 151.22 51 151.87 52 152.01 53 152.28 54 152.82 55 153.47 56 153.78 57 154.06 58 154.15 59 154.39 60 154.57

3.4.2. Mass spectrum of #1804C60Cl12.

Supplementary Figure 9: Mass spectrum of #1804C60Cl12.

12

3.4.3. IR spectrum of #1804C60Cl12.

Supplementary Figure 10: IR spectrum of #1804C60Cl12 recorded on a KBr crystal disc coated with the #1804C60Cl12 solid film.

3.4.4. UV-Vis spectrum of #1804C60Cl12.

Supplementary Figure 11: UV-Vis spectrum of #1804C60Cl12.

13

4. Relative Energy of C60 isomers and the related chlorinated

derivatives.

4.1. The top-5 most stable C60 isomers.

All 1812 C60 isomers were initially optimized by semi-empirical PM3 method using

Gaussian 98 programS4. Further optimizations of the first five most stable isomers

obtained at the PM3 level, as listed in Table S4, were performed with the generalized

gradient approximation (GGA) Perdew-Burke-Ernzerhof (PBE) density functional

method and all-electron double numerical plus polarization (DNP) basis set

implemented in Dmol3 packageS5-7. It is noteworthy that these top-5 most stable C60

isomers can be topologically connected via the well-known Stone-Wales

transformation (Fig. S12). Among them, the computation-optimal geometric XYZ

coordinates for the atoms of #1809C60 (C2v) and #1804C60 (Cs) are listed in Table S5.

Supplementary Figure 12: The PBE/DNP-optimized geometries of the top-5 most stable

C60 isomers. The carbon atoms of pentagon-pentagon fusions are colored in red. Stone-Wales (SW) transformations are indicated by blue dash circles and lines. The

carbon atoms involved in SW transformation are colored in blue.

14

Supplementary Table 4: The first five most stable C60 cage isomers. Relative energies and HOMO-LUMO gaps are denoted by ∆E (in kcal/mol) and Eg (in eV) respectively,

where the superscript PM3 or PBE indicate the computations are performed at the PM3 or PBE/DNP levels of theory.

Spiral Code a Symmetry Nc b ∆EPM3 Eg

PM3 ∆EPBE EgPBE

1812 Ih 0 0.00 6.59 0.00 1.67 1809 C2v 4 42.99 5.77 35.65 0.94 1804 Cs 6 65.96 5.74 53.15 0.99 1803 D3 6 67.16 5.71 53.17 0.99 1789 C2 6 78.54 5.13 64.89 0.23

a The C60 isomers are sorted based on the spiral algorithm. b The number of carbon atoms (Nc) of pentagon-pentagon fusions in the related C60 isomers.

Supplementary Table 5: The XYZ coordinates of #1809C60 and #1804C60 cages.

#1809C60 #1804C60

x y z x y z

-0.736284 0.736284 1.197330 0.000000 -1.197330 -1.182075 0.000000 1.182075 2.262547 2.828723 2.261260 2.261260 1.197330 0.000000 -1.197330 -2.261260 -2.261260 -2.828723 -2.262547 -2.289978 -1.176348 0.000000 1.176348 2.289978 2.988755 3.338727

2.666451 2.666451 1.418275 0.679904 1.418275 3.265546 3.683862 3.265546 2.660251 1.427784 0.736663 -0.736663 -1.418275 -0.679904 -1.418275 -0.736663 0.736663 1.427784 2.660251 2.622844 3.065527 3.566644 3.065527 2.622844 1.423406 0.693410

-2.584974 -2.584974 -3.028808 -3.449426 -3.028808 -1.382941 -0.626929 -1.382941 -0.718440 -1.217436 -2.332467 -2.332467 -3.028808 -3.449426 -3.028808 -2.332467 -2.332467 -1.217436 -0.718440 0.732278 1.459175 0.760537 1.459175 0.732278 1.137837 -0.069237

-1.058105 0.499582 0.499582 -1.894127 -2.175711 0.961053 -1.379394 0.419951 1.025176 -2.175711 2.156268 -1.027300 1.095076 -2.378216 2.297129 -0.755296 -0.006972 -2.378216 2.156268 0.961053 -0.006972 1.285088 -1.379394 1.579515 2.297129 -1.894127

1.519390 3.580542 3.580542 2.919457 0.991454 -1.582210 -1.312159 -2.711645 2.503874 0.991454 -0.985161 -2.581833 -3.216210 -0.465346 0.456415 3.362624 0.624214 -0.465346 -0.985161 -1.582210 0.624214 1.235077 -1.312159 2.918185 0.456415 2.919457

-3.051755 0.686571 -0.686571 0.731046 -2.314039 3.022276 2.863451 -2.303293 -2.655183 2.314039 -2.604224 -2.276776 -1.180471 -2.282050 2.646729 1.419802 -3.537293 2.282050 2.604224 -3.022276 3.537293 3.220226 -2.863451 1.425175 -2.646729 -0.731046

15

3.338727 2.828723 2.262547 1.182075 0.736284 -0.736284 -1.182075 -2.262547 -2.828723 -3.338727 -3.338727 -2.988755 -2.583873 -1.423716 -0.728033 0.728033

-0.693410 -1.427784 -2.660251 -3.265546 -2.666451 -2.666451 -3.265546 -2.660251 -1.427784 -0.693410 0.693410 1.423406 0.726045 1.176029 2.319663 2.319663

-0.069237 -1.217436 -0.718440 -1.382941 -2.584974 -2.584974 -1.382941 -0.718440 -1.217436 -0.069237 -0.069237 1.137837 2.281698 3.027462 2.616181 2.616181

0.419951 -0.160855 -0.755296 -3.127889 -2.611952 -2.611952 -1.058105 -2.862446 -1.750924 1.579515 -0.419967 -3.127889 -0.160855 2.529925 2.529925 -1.027300

-2.711645 -0.741469 3.362624 -1.026817 1.764765 1.764765 1.519390 -2.331981 -3.082339 2.918185 2.704256 -1.026817 -0.741469 2.075380 2.075380 -2.581833

2.303293 -3.417273 -1.419802 -1.191495 1.190642 -1.190642 3.051755 -0.732285 -1.181371 -1.425175 2.623148 1.191495 3.417273 -0.737044 0.737044 2.276776

4.2. Chlorofullerene C60Cl8

The quantum chemical computations of chlorofullerenes are also conducted at the

PBE/DNP level of theory. Two C60Cl8 isomers, #1812C60Cl8 and #1809C60Cl8, derived

from #1812C60 (Ih) and #1809C60 (C2v) carbon cages were considered. #1812C60Cl8,

assumed to be analogous to the explicitly determined C60Br8S8 synthesized by

bromination of Ih-C60, is 33.1 kcal/mol less stable than #1809C60Cl8 reported herein, and,

meanwhile, has a smaller HOMO-LUMO gap than the latter (Fig. S13).

Supplementary Figure 13: The PBE/DNP-optimized geometries of C60Cl8 isomers: a, #1809C60Cl8 and b, #1812C60Cl8. Relative energies (∆E) and HOMO-LUMO gaps (Eg) are

given in kcal/mol and eV, respectively.

16

4.3. [C60Cl7]+ intermediates

Geometries of the [C60Cl7]+ cationic intermediates in the Friedel-Craft reactions

were optimized at the PBE/DNP level of theory. The solvent effect of benzene was

then taken into account by means of the COnductor-like Screening MOdel

(COSMO)S9. The COSMO approach traps [C60Cl7]+ into a cavity of benzene

molecules represented by its dielectric continuum of permittivity (ε= 2.283 at 20

°C)S10. Finally, the PBE/DNP-COSMO optimizations were carried out for the

[C60Cl7]+ cations by using Dmol3 package.

The theoretical computations predicted that 1a is more stable than 1b in both gas

phase (13.25 kcal/mol) and benzene solvent (13.31 kcal/mol) (Fig. S14). Therefore,

the Chh-Cl bonds in #1809C60Cl8 are more likely to dissociate to form more stable 1a as

a cationic intermediate. These computational results agree very well with the

experimental observations that the Cpp-Cl bonds in #1809C60Cl8 always survive in the

Friedel-Crafts alkylation in spite of the 5 hours reaction at 80 °C.

Supplementary Figure 14: The PBE/DNP-COSMO optimized structures for [C60Cl7]+: (1a) of a heterolytic Chh-Cl dissociation, and (1b) of a heterolytic Cpp-Cl dissociation. Carbon atoms at pentagon-pentagon fusions are colored in red. Chh and Cpp carbon atoms are

indicated by blue arrows.

17

5. The curvature of the C60 cage surfaces.

The degree of cage curvature can be appreciated from the pyramidalization angle,

i.e., the π-orbital axis vector (POAV) angleS11, which is the angle between the virtual

π-orbital axis and its three adjacent C–C bonds minus 90°. The single POAV angle

in Ih–C60 is 11.64°. In comparison, the corresponding values for carbons located at

pentagon fusion (Cpp) are estimated to be respectively 15.00° and 15.07° on average

for #1809C60 and #1804C60. In contrast, the mean values of POAV angle for the other

carbon sites in #1809C60 and #1804C60 are predicted to be 11.47° and 11.30°, respectively,

similar to that of Ih–C60. The sizable POAV angle difference between Cpp and other

carbon sites of #1809C60 and #1804C60 suggests: 1) sizable strains at Cpp sites, and 2)

preferential bond formation at these sites, such as chlorination in the present case, for

strain relief. The effects of pentagon fusion are also seen in the bond angles and

distances involving the C–Cl bonds in the chlorinated derivatives. In 1, for instance,

the common bond angles of C–Cl with three neighboring C–C bonds are 113.2°

averaged for the four Cpp–Cl bonds, and 111.4° for the four Chh–Cl bonds at the

pentagon-hexagon-hexagon vertexes, while the Chh–Cl bonds are on average 0.04 Å

longer than the Cpp–Cl bonds. While in 2, the mean angle of C–Cl vs. adjacent C–C

bonds are 112.7o at Cpp and 111.2o at Chh sites. These noticeable metric differences

clearly indicate that the tetrahedral geometry about Cpp deviates more severely from a

regular tetrahedron than that of Chh. This also implies that the chlorinated species thus

obtained have maintained the structural “deformation” of their parental IPR-violated

cages from Ih–C60, especially at the pentagon fusion site. It follows that some

unusual properties of isomeric fullerenes originated from such “deformation” may be

retained in the chlorinated species.

6. Chemical reactivity and characterization of C60 isomer

derivatives.

6.1 Friedel-Crafts reactions.

6.1.1. Crystallographic characterization for #1809C60Cl4(C6H5)4.

18

Brown-red single crystals suitable for X-ray diffraction studies were obtained by

solvent evaporation from its yellow carbon disulfide solution.

A block of crystal with dimensions of 0.08 × 0.03 × 0.03 mm was selected for X-ray

diffraction. The diffraction date were collected on an Oxford CCD diffractometer

using a graphite-monochromated Cu Kα (λ = 1.54178 Å) radiation with ω scan mode

at 173 K. The crystal belongs to orthorhombic system, space group Pbcn with the cell

parameters: a = 29.974(4), b = 15.735(2), c = 20.264(3) Å, α = 90.00, β = 90.00, γ =

90.00°, V = 9557(2) Å3, Z = 8. A total of 44799 reflections were measured in the θ

range (3.85 ≤ θ ≤ 62.67) and 7561 were independent with Rint = 0.2340, of which

1998 were considered as observed (I > 2σ(I)). Lorentz-polarization and absorption

correction were applied. The structure was solved by direct methods with

SHELXS-97 program and refined by full-matrix least-squares calculations with

SHELXS-97 program based on F2 [S2, S3]. All non-hydrogen atoms were refined

anisotropically and the hydrogen atoms were added theoretically. The final full-matrix

least-squares refinement gave R = 0.0696 wR = 0.1435 (w =

1/[σ2(F02)+(0.0691P)2+0.0000P]), where P = (F0

2+2Fc2)/3, S = 0.810, (∆/α)max = 0.000,

(∆ρ)max = 1.480, (∆ρ)min= -0.537 e/Å3. CCDC-678134 contains the supplementary

crystallographic data for #1809C60Cl4(C6H5)4. These data can be obtained free of charge

from the Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

6.1.2. 1H NMR, IR, UV/Vis and MS data of #1809C60Cl4(C6H5)4.

6.1.2.1. 1H NMR spectrum of #1809C60Cl4(C6H5)4.

19

Supplementary Figure 15: 1H NMR spectrum of #1809C60Cl4(C6H5)4. The data were

acquired on a Bruker AV 600 instrument of 600.134 MHz after 15,360 scans at 25 oC under 30o exiting pulse with 2 s repetition time

6.1.2.2. Mass spectrum of #1809C60Cl4(C6H5)4.

Supplementary Figure 16: Mass spectrum of #1809C60Cl4(C6H5)4.

20

6.1.2.3. IR spectrum of #1809C60Cl4(C6H5)4.

Supplementary Figure 17: IR spectrum of #1809C60Cl4(C6H5)4 recorded on a KBr crystal

disc coated with #1809C60Cl4(C6H5)4 solid film.

6.1.2.4. UV/Vis spectrum of #1809C60Cl4(C6H5)4.

Supplementary Figure 18: UV/Vis spectrum of #1809C60Cl4(C6H5)4 measured in

toluene solution.

21

6.1.3. Synthesis and MS identification of #1809C60Cl4(C6H5)n(C6H4CH3)4–n

(n=0–4).

The reactions between 1 and benzene/toluene were carried out at two stages: (1) The

reaction between 1 (0.1 mg) and benzene (5 mL) was catalyzed with FeCl3 (2 mg) in

80 °C for 1 hour; (2) Part of the crude products (4 mL) from the first stage were

mixed with 4 mL toluene and 4 mg FeCl3 for further reaction in 80 oC for 5 hours.

The products from the two stages were separated on a Discovery ODS column (4.6

I.D. × 250 mm) eluted by a methanol/ethanol/cyclohexane gradient solvent in an

Agilent 1200 HPLC system, and identified with a Bruker Esquire HCT mass

spectrometer. Figs S19 and S20 show the HPLC-MS chromatograms in which the

products can be characterized as #1809C60Cl8–n(C6H5)n (n=1–4) at first step and #1809C60Cl4(C6H5)n(C6H4CH3)4–n (n=0–4) at another stage.

Supplementary Figure 19: HPLC-MS chromatogram of products from the reaction of

#1809C60Cl8 with C6H6. The corresponding mass spectra are separately inset.

22

Supplementary Figure 20: HPLC-MS chromatogram of the products from the

reaction of #1809C60Cl8 with benzene and toluene. The corresponding mass spectra are inset separately.

6.2. Nucleophilic reactions

6.2.1. HPLC-MS identification of #1809C60(CH3O)8

Supplementary Figure 21: HPLC-MS chromatogram of the products from the reaction of #1809C60Cl8 with CH3ONa. Inset is the mass spectrum of the main product.

23

6.2.2. HPLC-MS identification of #1809C60(C6H5CH2O)8

Supplementary Figure 22: HPLC-MS chromatogram of the products from the

reaction of #1809C60Cl8 with C6H5CH2ONa. Inset is the mass spectrum of the main product.

6.2.3. HPLC-MS identification of #1809C60Cl4(NHCH2COOCH3)4

Supplementary Figure 23: HPLC-MS chromatogram of the products from the reaction of #1809C60Cl8 with NH2CH2COOCH3. Insets are the corresponding mass spectra

of the products.

7. The MSn and thermal dechlorination results of #1804C60Cl12.

Similar to the experiments on 1, the existence of a C60 unit derived from 2 was also

proved using the multistage mass spectrometry (MSn) and the spray pyrolysis

24

experiment. Figs S24 and S25 show the MSn spectra and the thermal dechlorination

mass spectrum at 500 oC, respectively.

Supplementary Figure 24: Dechlorination of #1804C60Cl12. Multistage mass

spectrometry (MSn, n=1–5) showing progressive dechlorination of #1804C60Clm (m=0–12) (m value is indicated as number in blue circles and the species selected for next stage of

MS fragmentation are marked with green rhombic). m/z, mass to charge ratio.

Supplementary Figure 25: Thermal dechlorination of #1804C60Cl12. The numbers of

chlorine atoms in the dechlorinated species are indicated in blue circles.

25

8. The yield correlation among #1809C60Cl8, Ih-C60 and D5h-C70.

The product mixture obtained from the arc-discharge of graphite contains fullerenes

(e.g., Ih-#1812C60, D5h-#8149C70), chlorinated fullerenes, and other compounds. Yields

of individual components vary with the reaction conditions, as indicated by the HPLC

chromatograms of a series of crude products (Fig. S26). The peak area corresponds

to the yield of that particular component, and a comparison of which reveals an

interesting correlation between the relative yields of #1809C60Cl8, Ih-C60 and D5h-C70.

Specifically, as the yield of #1809C60Cl8 decreases, that of Ih-C60 increases, in an

essentially linear fashion. While the yield of D5h-C70 also increases, the reason is

unclear at this stage. This may suggest a relationship between these two C60 species,

possibly by isomerization.

Supplementary Figure 26: HPLC chromatograms (360 nm) of five crude products. Insets are the peak areas correlations of #1809C60Cl8 vs. Ih-C60 and D5h-C70 vs. Ih-C60.

26

9. The full list of Refs 13, 19, 21, 25, 26, and 30

Ref 13. Xie, S. Y., Gao, F., Lu, X., Huang, R. B., Wang, C. R., Zhang, X., Liu, M.

L. , Deng, S. L. & Zheng, L. S. Capturing the labile fullerene[50] as C50Cl10. Science

304, 699–699 (2004)

Ref 19. Han, X., Zhou, S. J., Tan, Y. Z., Wu, X., Gao, F., Liao, Z. J., Huang, R. B.,

Feng, Y. Q., Lu, X., Xie, S. Y., & Zheng, L. S. Crystal Structures of Saturn-Like

C50Cl10 and Pineapple-Shaped C64Cl4 : Geometric Implications of Double- and

Triple-Pentagon-Fused Chlorofullerenes. Angew. Chem. Int. Ed. 47, 5340–5343

(2008).

Ref 21. Troshin. P. A., Avent, A. G., Darwish, A. D., Martsinovich, N., Abdul-Sada,

A. K., Street, J. M., & Taylor, R. Isolation of two seven-membered ring C58 fullerene

derivatives: C58F17CF3 and C58F18. Science 309, 278–281 (2005).

Ref 25. Avent, A. G Avent, A. G., Birkett, P. R., Crane, J. D., Darwish, A. D.,

Langley, G. J., Kroto, H. W., Taylor, R., Walton, D. R. M. The structure of C60Ph5Cl

and C60Cl5H, formed via electrophilic aromatic substitution. J. Chem. Soc., Chem.

Commun. 1994, 1463–1464 (1994)

Ref 26. Birkett, P. R., Avent, A. G., Darwish, A. D., Hahn, I., Kroto, H. W., Langley,

G. J., OLoughlin, J., Taylor, R., Walton, D. R. M. Arylation of [60]fullerene via

electrophilic aromatic substitution involving the electrophile C60Cl6: frontside

nucleophilic substitution of fullerenes . J. Chem. Soc., Perkin Trans. 2. 1997,

1121–1125 (1997).

Ref 30. Suenaga, K., Wakabayashi, H., Koshino, M., Sato, Y., Urita, K. & Iijima, S.

Imaging active topological defects incarbon nanotubes. Nature nanotechnology. 2,

27

358–360 (2007).

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