Supporting Information for. an Equatorial Diadduct: Evidence for an Electrophilic Carbanion

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1 Supporting Information for Controlled Synthesis of C 70 Equatorial Multiadducts with Mixed Addends from an Equatorial Diadduct: Evidence for an Electrophilic Carbanion Shu-Hui Li, Zong-Jun Li,* Wei-Wei Yang, and Xiang Gao* State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin , P. R. China * lzj@ciac.ac.cn, xgao@ciac.ac.cn Table of Contents Experimental details and spectral characterization of compounds 1 3 Figure S1. HPLC trace of the crude mixture from the reaction for preparation of 1a Figure S2. HPLC trace of the crude mixture from the reaction for preparation of 1b Figure S3. HPLC trace of the crude mixture from the reaction for preparation of 2a Figure S4. HPLC trace of the crude mixture from the reaction for preparation of 2b Figure S5. HPLC trace of the crude mixture from the control reaction of 7,23-Bn 2 C 70 S6 S17 S18 S19 S20 S21 with 3.1 equiv of MeO (in one shot) followed by quenching with o-brch 2 PhCH 2 Br Figure S6. HPLC trace of the crude mixture from the reaction for preparation of 3a Figure S7. HPLC trace of the crude mixture from the reaction for preparation of 3b Figure S8. (a) Structural illustration of 2a-II; (b) HPLC trace of the crude mixture S22 S23 S24 from the control experiment demonstrating the stability of 2a-II over a Buckyprep column S1

2 Figure S9. HPLC trace of the crude mixture from the control experiment S25 demonstrating the stability of 2a-II over a silica column Figure S10. Positive ESI FT-ICR MS of 1a Figure S11. 1 H NMR spectrum of 1a Figure S C NMR spectrum of 1a Figure S13. UV-vis absorption spectrum of 1a Figure S14. Positive ESI FT-ICR MS of 1b Figure S15. 1 H NMR spectrum of 1b Figure S C NMR spectrum of 1b Figure S17. UV-vis absorption spectrum of 1b Figure S18. Positive ESI FT-ICR MS of 2a Figure S19. 1 H NMR spectrum of 2a Figure S C NMR spectrum of 2a Figure S21. UV-vis absorption spectrum of 2a Figure S22. Positive ESI FT-ICR MS of 2b Figure S23. 1 H NMR spectrum of 2b Figure S C NMR spectrum of 2b Figure S25. UV-vis absorption spectrum of 2b Figure S26. Positive ESI FT-ICR MS of 3a Figure S27. 1 H NMR spectrum of 3a Figure S C NMR spectrum of 3a Figure S29. UV-vis absorption spectrum of 3a S26 S27 S28 S29 S30 S31 S32 S33 S34 S35 S36 S37 S38 S39 S340 S41 S42 S43 S44 S45 S2

3 Figure S30. Positive ESI FT-ICR MS of 3b Figure S31. 1 H NMR spectrum of 3b Figure S C NMR spectrum of 3b Figure S33. (a) UV-vis absorption and (b) mirror image of the fluorescence and S46 S47 S48 S49 absorption spectra of 3b Figure S34. Positive MALDI TOF MS of 2a and 2a-II mixture Figure S35. 1 H NMR spectrum of 2a and 2a-II mixture Figure S36. UV-vis absorption spectrum of 2a-II Figure S37. In situ vis-nir of control methoxylation experiment with 1,4-Bn 2 C 60 Figure S38. Partial electrophilic Fukui function (f + k ) distribution in 7,23-Bn 2 C 70 S50 S51 S52 S53 S54 calculated at the B3LYP/6-311G(d) level Table S1. Electrophilic Fukui indexes (f k + ) for C 70 carbon atoms in 7,23-Bn 2 C 70 S55 calculated at the B3LYP/6-311G(d) level Figure S39. Partial electrophilic Fukui function (f k + ) distribution in intermediate A S57 calculated at the B3LYP/6-311G(d) level Table S2. Electrophilic Fukui indexes (f k + ) for C 70 carbon atoms in intermediate A S58 calculated at the B3LYP/6-311G(d) level Figure S40. Partial electrophilic Fukui function (f k + ) distribution in S60 1,4-Bn 2-11-MeOC 60 calculated at the B3LYP/6-311G(d) level Table S3. Electrophilic Fukui indexes (f k + ) for C 60 carbon atoms in S61 1,4-Bn 2-11-MeOC 60 calculated at the B3LYP/6-311G(d) level Figure S41. Partial NBO charge distribution in intermediate A calculated at the S63 S3

4 B3LYP/6-311G(d) level Table S4. NBO charge distribution for C 70 carbon cage in intermediate A calculated at S64 the B3LYP/6-311G(d) level Figure S42. Partial NBO charge distributions in intermediate B calculated at the S66 B3LYP/6-311G(d) level Table S5. NBO charge distribution for C 70 carbon cage in intermediate B calculated at S67 the B3LYP/6-311G(d) level Figure S43. Partial electrophilic Fukui function (f k + ) distribution in compound 2a S69 calculated at the B3LYP/6-311G(d) level Table S6. Electrophilic Fukui function (f k + ) distribution for C 70 carbon cage in S70 compound 2a calculated at the B3LYP/6-311G(d) level Figure S44. Partial NBO charge distributions in intermediate C calculated at the S72 B3LYP/6-311G(d) level Table S7. NBO charge distributions for C 70 carbon cage in intermediate C calculated S73 at the B3LYP/6-311G(d) level Optimized structure, cartesian coordinates and the lowest frequency for 7,23-Bn 2 C 70 S75 obtained at B3LYP/6-31G level Optimized structure, cartesian coordinates, the lowest frequency, and sum of S78 electronic and zero-point energies for intermediate A obtained at B3LYP/6-31G level Optimized structure, cartesian coordinates, the lowest frequency, and sum of S81 electronic and zero-point energies for the isomer of intermediate A obtained at B3LYP/6-31G level S4

5 Optimized structure, cartesian coordinates and the lowest frequency for S84 1,4-Bn 2-11-MeOC 60 obtained at B3LYP/6-31G level Optimized structure, cartesian coordinates and the lowest frequency for intermediate S87 B obtained at B3LYP/6-31G level Optimized structure, cartesian coordinates and the lowest frequency for 2a obtained at S90 B3LYP/6-31G level Optimized structure, cartesian coordinates and the lowest frequency for intermediate S94 C obtained at B3LYP/6-31G level S5

6 General Methods. All reactions were carried out under an atmosphere of argon. All reagents were obtained commercially and used without further purification, unless otherwise noted. All spectral measurements were carried out in 1-cm quartz cuvettes. In situ vis-near-ir spectra were measured by first transferring the reaction mixture into a 1-cm cuvette under argon, and the cuvette was sealed with a rubber septum and Parafilm for the measurement. The fluorescence spectra were recorded with the excitation and the emission slit widths set at 10 and 20 nm, respectively. All solvents used in fluorescence spectra studies were of spectroscopic grade. Preparation of Compound 1a. Typically, 30.3 mg of 7,23-Bn 2 C 70 (29.6 μmol) was put into 30 ml of o-dcb solution at 30 C, which was degassed with argon for 20 min under vigorous stirring. Then 1.1 equiv of MeO (1.0 M TBAOH in methanol, 32.6 L, 32.6 μmol) was added in to the 7,23-Bn 2 C 70 o-dcb solution to react for 1.5 h with no significant color change. The reaction mixture was quenched with 50 equiv of o-brch 2 PhCH 2 Br (391.3 mg, 1.48 mmol) for 3 h, and the mixture was dried with a rotary evaporator under reduced pressure. The residue was washed with methanol to remove excess TBAOH and o-brch 2 PhCH 2 Br. The crude product was put into toluene, and the dissolved part was purified using a semipreprative Buckyprep column (10 mm 250 mm) eluted with toluene at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. Compound 1a was obtained with an isolated yield of 49% (18.0 mg), along with 8.1 mg of unreacted 7,23-Bn 2 C 70. Spectral Characterization of 1a: Positive ESI FT-ICR MS: calcd for [M CH 3 O] + (C 92 H 22 Br) + : , found ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) ppm, (m, 11H), (m, 3H), 4.78 (d, J = 10.2 Hz, 1H), 4.36 (d, J = 10.2 Hz, 1H), 3.97 (d, J = 12.6 Hz, 1H), 3.95(d, J = 12.0 Hz, 1H), 3.91 (d, J = 13.2 Hz, 1H), 3.85 (d, J = 13.2 Hz, 1H), 3.82 (d, J S6

7 =13.2 Hz, 1H), 3.75 (s, 3H), 3.73 (d, J = 14.4 Hz, 1H); 13 C NMR (150 MHz, CS 2 /CDCl 3 ) δ ppm, (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (2C), (1C), (1C, Ph), (1C), (1C, Ph), (4C, Ph), (1C), (2C, Ph), (2C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, sp 3, C 70 O), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, O CH 3 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ); UV-vis (toluene): max 365, 400, 450, 539 and 605 nm. X-ray Single Crystal Diffraction of 1a. Black crystals of 1a were obtained by slowly diffusing methanol into a CS 2 solution of 1a at room temperature. Single crystal X-ray diffraction data were collected on an instrument equipped with a CCD area detector using graphite-monochromated Mo Kα radiation (λ = Å) in the scan range 1.68 < θ < The structure was solved with the direct method of SHELXS-97 and refined with full-matrix least-squares techniques using the SHELXL-97 program within WINGX. Crystal data of 1a C 93 H 25 BrO, M w = , Triclinic, space group P-1, a = (2) Å, b = (3)) Å, c = (4) (14) Å, α = (4), β = (4), γ = (3), V = (11) (6) Å 3, Z = 2, D calcd S7

8 = Mg m 3, μ= mm 1, T = 188 (2) K, crystal size mm; reflections collected 12901, independent reflections 9273; 4200 with I > 2σ (I); R1 = [I > 2σ (I)], wr2 = [I > 2σ (I)]; R1 = (all data), wr2 = (all data), GOF (on F 2 ) = Preparation of Compound 1b. The procedures were similar to those for generation of 1a, except PhCH 2 Br was used instead of o-brch 2 PhCH 2 Br. Compound 1b was obtained as the predominant product with an isolated yield of 46% (20.7 mg), along with 5.0 mg of unreacted 7,23-Bn 2 C 70. Spectral Characterization of 1b: Positive ESI FT-ICR MS, m/z calcd for [M CH 3 O] + (C 91 H + 21 ): , found ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) δ ppm, (m, 10H), (m, 4H), 4.00 (d, J = 13.2 Hz, 1H), 3.94 (d, J = 13.2 Hz, 1H), (m, 5H), 3.76 (d, J = 12.6 Hz, 1H), 3.62 (d, J = 13.8 Hz, 1H); 13 C NMR (150 MHz, CS 2 /CDCl 3 ) δ ppm, (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (4C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C, Ph), (1C, Ph), (1C, Ph), (1C), (1C), (1C), (1C), (1C), (1C), (4C, Ph), (2C, Ph), (1C), (2C, Ph), (1C), (2C, Ph), (2C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (sp 3, C 70 O), (sp 3, S8

9 C 70 CH 2 ), (sp 3, C 70 CH 2 ), (sp 3, C 70 CH 2 ), (O CH 3 ), (CH 2 ), (CH 2 ), (CH 2 ); UV vis (toluene): λ max 365, 400, 450, 539 and 605 nm. Preparation of Compound 2a. Typically, 30.5 mg of 7,23-Bn 2 C 70 (29.8 μmol) was put into 30 ml of o-dcb solution at 30 C, which was degassed with argon for 20 min under vigorous stirring. Then 2.1 equiv of MeO (1.0 M TBAOH in methanol, 62.7 L, 62.7 μmol) was added in to the 7,23-Bn 2 C 70 o-dcb solution to react for 1.5 h, accompanied by a gradual color change of the solution from brown to dark-green. The reaction mixture was quenched with 50 equiv of o-brch 2 PhCH 2 Br (393.9 mg, 1.49 mmol) for 3 h, and the mixture was dried with a rotary evaporator under reduced pressure. The residue was washed with methanol to remove excess TBAOH and o-brch 2 PhCH 2 Br. The crude product was put into toluene, and the dissolved part was purified using a semipreprative Buckyprep column (10 mm 250 mm) eluted with toluene at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. Compound 2a was obtained with an isolated yield of 53% (22.9 mg), along with 5.7 mg of unreacted 7,23-Bn 2 C 70. Spectral Characterization of 2a: Positive ESI FT-ICR MS: calcd for [M CH 3 O] + (C 101 H 33 Br 2 O + ): , found ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) δ ppm, (d, 2H), (m, 8H), (m, 2H), (m, 2H), (m, 4H), 4.90 (d, J = 10.8 Hz, 2H), 4.39 (d, J = 10.2 Hz, 2H), 4.04 (d, J = 13.2 Hz, 2H), (m, 6H), 3.73 (s, 6H); 13 C NMR (150 MHz, CS 2 /CDCl 3 ) δ ppm, (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (4C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C, Ph), S9

10 (2C, Ph), (4C, Ph), (4C, Ph), (2C, Ph), (2C, Ph), (2C, Ph), (2C, sp 3, C 70 O), (2C, sp 3, C 70 CH 2 ), (2C, sp 3, C 70 CH 2 ), (2C, O CH 3 ), (2C, CH 2 ), (2C, CH 2 ), (2C, CH 2 ); UV-vis (toluene): max 410, 449, 475, 562, 650 and 716 nm. X-ray Single Crystal Diffraction of 2a. Black crystals of 2a were obtained by slowly diffusing n-hexane into a CS 2 solution of 2a at room temperature. Single crystal X-ray diffraction data were collected on an instrument equipped with a CCD area detector using graphite-monochromated Mo Kα radiation (λ = Å) in the scan range 1.49 < θ < The structure was solved with the direct method of SHELXS-97 and refined with full-matrix least-squares techniques using the SHELXL-97 program within WINGX. Crystal data of 2a CS 2 ; C 103 H 36 Br 2 O 2 S 2, M w = , Triclinic, space group P 1, a = (6) Å, b = (9) Å, c = (11) Å, α = (10), β = (10), γ = (10), V = (3) Å 3, Z = 2, D calcd = Mg m 3, μ= mm 1, T = 187 (2) K, crystal size mm; reflections collected 18717, independent reflections 12954; 8011 with I > 2σ (I); R1 = [I > 2σ (I)], wr2 = [I > 2σ (I)]; R1 = (all data), wr2 = (all data), GOF (on F 2 ) = Preparation of Compound 2b. The procedures were similar to those for generation of 2a, except PhCH 2 Br was used instead of o-brch 2 PhCH 2 Br. Compound 2b was obtained as the predominant product with an isolated yield of 40% (18.5 mg), along with 4.4 mg of unreacted 7,23-Bn 2 C 70. Spectral Characterization of 2b: Positive ESI FT-ICR MS: calcd for M + (C 100 H 34 O + 2 ): , found ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) δ ppm, (m, 5H), (m, 15H), 4.02, 3.99 (ABq, 4H, J AB = 13.8 Hz), (m, 8H), 3.80 (d, 2H, J AB = S10

11 12.6 Hz); 13 C NMR (150 MHz, CS 2 /CDCl 3 ) δ ppm, (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C, Ph), (2C, Ph), (2C), (4C, Ph), (4C, Ph), (2C), (4C, Ph), (4C, Ph), (2C, Ph), (2C, Ph), (2C, sp 3, C 70 O), (2C, sp 3, C 70 CH 2 ), (2C, sp 3, C 70 CH 2 ), (2C, O CH 3 ), (2C, CH 2 ), (2C, CH 2 ); UV vis (toluene): max 410, 449, 475, 562, 650 and 716 nm. Control Experiment of 7,23-Bn 2 C 70 with 3.1 Equiv of MeO in One Shot. The procedures were similar to that for generation of 2a, except 3.1 equiv of MeO was used instead of 2.1 equiv of MeO. The result is similar to that when 2.1 equiv of MeO was used, where the major product is the hexaadduct 2a. Preparation of Compound 3a. Typically, 19.7 mg of 7,23-Bn 2 C 70 (19.3 μmol) was put into 20 ml of o-dcb solution at 30 C, which was degassed with argon for 20 min under vigorous stirring. Then 2.1 equiv of MeO (1.0 M TBAOH in methanol, 40.5 L, 40.5 μmol) was added in to the 7,23-Bn 2 C 70 o-dcb solution to react for 1.5 h, accompanied by a gradual color change of the solution from brown to dark-green. o-brch 2 PhCH 2 Br (50 equiv, mg, 0.96 mmol) was added into the reaction mixture to react for 3 h, with the formation of 2a. Then 1.1 equiv of MeO (1.0 M TBAOH in methanol, 21.2 L, 21.2 μmol) was added into this in situ generated 2a solution and reacted for 2 h. The mixture was dried with a rotary evaporator under reduced pressure, and the residue was washed with methanol to remove excess TBAOH and o-brch 2 PhCH 2 Br. The crude S11

12 product was put into toluene, and the dissolved part was purified using a semipreprative Buckyprep column (10 mm 250 mm) eluted with toluene at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. Compound 3a was obtained with an isolated yield of 41% (13.3 mg), along with 4.1 mg of unreacted 7,23-Bn 2 C 70. Spectral Characterization of 3a: Positive ESI FT-ICR MS: calcd for M + (C 111 H 47 Br 3 O + 3 ): , found ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) δ ppm, (m, 2H), (m, 4H), (m, 12H), (m, 4H), 4.95, 4.94 (ABq, J = 7.2 Hz, 2H), 4.86 (d, J = 10.8 Hz, 1H), 4.50 (d, J = 9.0 Hz, 1H), 4.42 (d, J = 10.2 Hz, 1H), 4.38 (d, J = 10.8 Hz, 1H), 4.18 (d, J = 13.8 Hz, 1H), (m, 6H), (m, 5H), 3.93 (d, J = 13.8 Hz, 1H), 3.88 (s, 3H), 3.62 (s, 3H); 13 C NMR (150 MHz, CS 2 /CDCl 3 ) δ ppm, (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (3C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (2C, Ph), (2C, Ph), (2C, Ph), (3C, Ph), (2C, Ph), (1C, Ph), (1C, Ph), (2C, Ph), (1C, Ph), (1C, Ph), (1C, sp 3, C 70 O), (1C, sp 3, C 70 O), (1C, sp 3, S12

13 C 70 O), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, O CH 3 ), (1C, O CH 3 ), (1C, O CH 3 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (2C, CH 2 ); UV-vis (toluene): max 390, 430, 455 and 502 nm. X-ray Single Crystal Diffraction of 3a. Orange crystals of 3a were obtained by slowly diffusing ethanol into a CS 2 solution of 3a at room temperature. Single crystal X-ray diffraction data were collected on an instrument equipped with a CCD area detector using graphite-monochromated Mo Kα radiation (λ = Å) in the scan range 1.44 < θ < The structure was solved with the direct method of SHELXS-97 and refined with full-matrix least-squares techniques using the SHELXL-97 program within WINGX. Crystal data of 3b; C 111 H 47 Br 3 O 3, M w = , Triclinic, space group P-1, a = (3) (11) Å, b = (3) Å, c = (4) Å, α = (3), β = (4), γ = (3), V = (15) Å 3, Z = 2, D calcd = Mg m 3, μ= mm 1, T = 188 (2) K, crystal size mm; reflections collected 22710, independent reflections 16462; 8139 with I > 2σ (I); R1 = [I > 2σ (I)], wr2 = [I > 2σ (I)]; R1 = (all data), wr2 = (all data), GOF (on F 2 ) = Preparation of Compound 3b. The procedures were similar to those for generation of 3a, except PhCH 2 Br was used instead of o-brch 2 PhCH 2 Br. Compound 3b was obtained as the predominant product with an isolated yield of 34% (12.2 mg), along with 4.5 mg of unreacted 7,23-Bn 2 C 70. Spectral Characterization of 3b: Positive ESI FT-ICR MS: calcd for M + (C 108 H 44 O + 3 ): , found ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) δ ppm, (m, 25H), (m, 3H), 4.04 (d, J = 13.2 Hz, 1H), (m, 8H), (m, 7H); 13 C NMR (150 S13

14 MHz, CS 2 /CDCl 3 ) δ ppm, (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (4C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (4C), (1C), (1C), (1C), (2C), (1C), (1C), (2C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (2C), (1C), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (1C, Ph), (4C, Ph), (2C, Ph), (2C, Ph), (2C, Ph), (2C, Ph), (2C, Ph), (4C, Ph), (2C, Ph), (1C, Ph), (1C, Ph), (2C, Ph), (1C, Ph), (1C, sp 3, C 70 O), (1C, sp 3, C 70 O), (1C, sp 3, C 70 O), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (1C, sp 3, C 70 CH 2 ), (2C, O CH 3 ), (1C, O CH 3 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ); UV-vis (toluene): max 390, 430, 455 and 502 nm. Control Experiment Showing the Existence of Another Stable Hexaadduct (2a-II). 7,23-Bn 2 C 70 (23.5 mg, 23.0 μmol) was put into 20 ml of o-dcb solution at 30 C, which was degassed with argon for 20 min under vigorous stirring. Then 1.1 equiv of MeO (1.0 M TBAOH in methanol, 25.3 L, 25.3 μmol) was added in to the 7,23-Bn 2 C 70 o-dcb solution to react for 1.5 h, followed by addition of 50 equiv of o-brch 2 PhCH 2 Br (303.5 mg, 1.15 mmol) into the reaction mixture to react for 3 h, with the formation of 1a. Then 1.0 equiv of MeO (1.0 M TBAOH in methanol, 23.0 L, 23.0 μmol) was added into the in situ generated 1a solution and the reaction was S14

15 continued for another 2 h. A mixture of hexaadducts was obtained (Figures S8 and S9) along with a significant amount of octaadduct(s) and 1a. The (RR') n C 70 (n = 6 or 8) obtained in this manner should be formed via the addition to (RR') n 2 C 70 precursors, rather than direct reaction of 7,23-Bn 2 C 70. The mixture of the hexaadducts could not be separated when eluting over a Buckyprep column with toluene (Figure S8), but could be partially resolved into two fractions when eluting over a silica column with a mixture of 70:30 v/v toluene/hexane (Figure S9). The 1 H NMR (Figure S35) confirmed the formation of two regioisomeric hexaadducts. Four sets of doublets with equal intensity were shown in the region of ppm, which corresponded to the two sets of nonequivalent Br-bound methylene protons by comparing the spectra of 1a and 1b, in agreement with the formation of 2a-II with C 1 symmetry. The spectrum also exhibited two doublets at 4.90 and 4.38 ppm, confirming the formation of 2a with the C 2 symmetry. However, the peak intensity of 2a is lower than that of 2a-II, indicating that 2a is less favored compared with 2a-II for hexaaddition when starting from the tetraadduct. Spectral Characterizations of 2a and 2a-II Mixture: Positive MALDI TOF MS: m/z calculated for [M + H] + (C 102 H 36 Br 2 O 2 + H) + : , found: ; 1 H NMR (600 MHz, CS 2 /CDCl 3 ) δ ppm, (m), (m), (m), (m), (m), 4.90 (d, J = 9.6 Hz), 4.88 (d, J = 9.6 Hz) 4.75 (d, J = 10.2 Hz), 4.45(d, J = 10.8 Hz), 4.38 (d, J = 10.8 Hz), 4.33(d, J = 10.2 Hz), 4.17 (d, J = 12.6 Hz), 4.11 (d, J = 13.2 Hz), 4.10 (d, J = 13.2 Hz), 4.04(d, 13.2 Hz), (m), 3.94 (s), 3.85 (d, J = 13.8 Hz), 3.73 (s), 3.68 (s); UV-vis (toluene): max 410, 449, 475, 562, 650 and 716 nm. Computational Details. All calculations were performed with the Gaussian 09 software package. All geometries were optimized at the DFT B3LYP/6-31G level of theory, and sum of S15

16 electronic and zero-point energies for intermediate A and its isomer were obtained at the same level. The electrophilic Fukui function (f k + ) distributions of 7,23-Bn 2 C 70, intermediate A, 1,4-Bn 2-11-MeOC 60 and 2a were calculated at B3LYP/6-311G(d,p) level. NBO charge distributions for intermediate A, B and C were performed at B3LYP/6-311G(d,p) level. S16

17 1a 7,23-Bn 2 C Time (min) Figure S1. HPLC trace of the crude mixture from the reaction for preparation of 1a. The crude product was eluted with toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S17

18 1b 7,23-Bn 2 C Time (min) Figure S2. HPLC trace of the crude mixture from the reaction for preparation of 1b. The crude product was eluted with toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S18

19 2a 7,23-Bn 2 C Time (min) Figure S3. HPLC trace of the crude mixture from the reaction for preparation of 2a. The crude product was eluted with toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S19

20 2b 7,23-Bn 2 C Time (min) Figure S4. HPLC trace of the crude mixture from the reaction for preparation of 2b. The crude product was eluted with toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S20

21 2a 1a 7,23-Bn 2 C Time (min) Figure S5. HPLC trace of the crude mixture from the control reaction of 7,23-Bn 2 C 70 with 3.1 equiv of MeO (one shot) followed by quenching with o-brch 2 PhCH 2 Br. The crude product was eluted with toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S21

22 3a 7,23-Bn 2 C Time (min) Figure S6. HPLC trace of the crude mixture from the reaction for preparation of 3a. The crude mixture was eluted by toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S22

23 3b 7,23-Bn 2 C Time (min) Figure S7. HPLC trace of the crude mixture from the reaction for preparation of 3b. The crude mixture was eluted by toluene over a semi-preparative Buckyprep column at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S23

24 (a) (a) (b) octaadduct(s) 2a-II and 2a 1a 7,23-Bn 2 C Time (min) Figure S8. (a) Structural illustration of 2a-II. (b) HPLC trace of the crude mixture from the control experiment demonstrating the stability of 2a-II over a semi-preparative Buckyprep column. The crude mixture was eluted by toluene at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S24

25 octaadduct(s) 2a-II 2a 1a 7,23-Bn 2 C Time (min) Figure S9. HPLC trace of the crude mixture from the control experiment showing the stability of 2a-II over a semi-preparative silica column. The mixture was eluted with a 70:30 v/v mixture of toluene/hexane at a flow rate of 3.7 ml/min with the detector wavelength set at 380 nm. S25

26 Figure S10. Positive ESI FT-ICR MS of compound 1a. S26

27 Figure S11. 1 H NMR spectrum (600 MHz) of compound 1a recorded in CS 2 /CDCl 3. The resonance at 1.4 ppm is due to H 2 O residue in the solvent, and the resonance at around 1.3 ppm is due to an unknown impurity. S27

28 Figure S C NMR spectrum (150 MHz) of 1a in CS 2 /CDCl 3. S28

29 Absorption Wavelength (nm) Figure S13. UV-vis absorption spectrum of compound 1a in toluene. S29

30 Figure S14. Positive ESI FT-ICR MS of compound 1b. S30

31 Figure S15. 1 H NMR spectrum (600 MHz) of compound 1b recorded in CS 2 /CDCl 3. The resonances at around 0.9 and 1.3 ppm are due to unknown impurities. S31

32 Figure S C NMR spectrum (150 MHz) of 1b in CS 2 /CDCl 3. S32

33 Absorption Wavelength (nm) Figure S17. UV-vis absorption and fluorescence spectra of compound 1b in toluene. S33

34 Figure S18. Positive ESI FT-ICR MS of compound 2a. S34

35 Figure S19. 1 H NMR spectrum (600 MHz) of compound 2a recorded in CS 2 /CDCl 3. S35

36 Figure S C NMR spectrum (150 MHz) of 2a in CS 2 /CDCl 3. S36

37 Absorption Wavelength (nm) Figure S21. UV-vis absorption and fluorescence spectra of compound 2a in toluene. S37

38 Figure S22. Positive ESI FT-ICR MS of compound 2b. S38

39 Figure S23. 1 H NMR spectrum (600 MHz) of compound 2b recorded in CS 2 /CDCl 3. The resonances at around 0.9 and 1.3 ppm are due to unknown impurities. S39

40 Figure S C NMR spectrum (150 MHz) of 2b in CS 2 /CDCl 3. S40

41 Absorption Wavelength (nm) Figure S25. UV-vis absorption spectrum of compound 2b in toluene. S41

42 Figure S26. Positive ESI FT-ICR MS of compound 3a. S42

43 Figure S27. 1 H NMR spectrum (600 MHz) of compound 3a recorded in CS 2 /CDCl 3. S43

44 Figure S C NMR spectrum (150 MHz) of 3a in CS 2 /CDCl 3. S44

45 Absorption Wavelength (nm) Figure S29. UV-vis absorption spectrum of compound 3a in toluene. S45

46 Figure S30. Positive ESI FT-ICR MS of compound 3b. S46

47 Figure S31. 1 H NMR spectrum (600 MHz) of compound 3b recorded in CS 2 /CDCl 3. S47

48 Figure S C NMR spectrum (150 MHz) of 3b in CS 2 /CDCl 3. S48

49 (a) Absorption Wavelength (nm) (b) absorption fluorescence Wavelength (nm) Figure S33. (a) UV-vis absorption and (b) mirror image of the fluorescence (red line) and absorption spectra (black line) of compound 3b in toluene. S49

50 Figure S34. Positive MALDI TOF MS of the Buckyprep HPLC fraction containing 2a-II and 2a. S50

51 Figure S35. 1 H NMR spectrum (600 MHz) of the Buckyprep HPLC fraction containing 2a-II and 2a recorded in CS 2 /CDCl 3. S51

52 Absorption Wavelength (nm) Figure S36. UV-vis absorption spectrum of compound 2a-II in toluene. S52

53 a b c Absorption Wavelength (nm) Figure S37. In situ vis-nir spectra of (a) 1,4-Bn 2 C 60 ( M), (b) 1,4-Bn 2 C 60 ( M) after mixing with 1.0 equiv of MeO for 1.5 h, and (c) 1,4-Bn 2 C 60 ( M) after mixing with 2.1 equiv of MeO for 1.5 h. The measurements were performed with a 1-cm cuvette in o-dcb at 30 C under argon. S53

54 Figure S38. Partial electrophilic Fukui function (f k + ) distribution in 7,23-Bn 2 C 70 calculated at the B3LYP/6-311G(d) level. S54

55 Table S1. Electrophilic Fukui indexes (f k + ) for C 70 carbon atoms in 7,23-Bn 2 C 70 calculated at the B3LYP/6-311G(d) level. Atomic number in Figure S38 Atomic number in the cartesian coordinates Fukui Index S55

56 S56

57 Figure S39. Partial electrophilic Fukui function (f k + ) distribution in intermediate A calculated at the B3LYP/6-311G(d) level. S57

58 Table S2. Electrophilic Fukui indexes (f k + ) for C 70 carbon atoms in intermediate A calculated at the B3LYP/6-311G(d) level. Atomic number in Figure S39 Atomic number in the Cartesian coordinates Fukui Index S58

59 S59

60 Figure S40. Partial electrophilic Fukui function (f k + ) distribution in 1,4-Bn 2-11-MeOC 60 calculated at the B3LYP/6-311G(d) level. S60

61 Table S3. Electrophilic Fukui indexes (f k + ) for C 60 carbon atoms in 1,4-Bn 2-11-MeOC 60 calculated at the B3LYP/6-311G(d) level. Atomic number in Figure S40 Atomic number in the Cartesian coordinates Fukui Index S61

62 S62

63 Figure S41. Partial NBO charge distribution in intermediate A calculated at the B3LYP/6-311G(d) level. S63

64 Table S4. NBO charge distribution for C 70 carbon cage in intermediate A calculated at the B3LYP/6-311G(d) level Atomic number in Figure S41 Atomic number in the cartesian coordinates Charge S64

65 S65

66 Figure S42. Partial NBO charge distributions in intermediate B calculated at the B3LYP/6-311G(d) level. S66

67 Table S5. NBO charge distribution for C 70 carbon cage in intermediate B calculated at the B3LYP/6-311G(d) level. Atomic number in Figure S42 Atomic number in the cartesian coordinates Charge S67

68 S68

69 Figure S43. Partial electrophilic Fukui function (f k + ) distribution in compound 2a calculated at the B3LYP/6-311G(d) level. S69

70 Table S6. Electrophilic Fukui function (f k + ) distribution for C 70 carbon cage in compound 2a calculated at the B3LYP/6-311G(d) level. Atomic number in Figure S43 Atomic number in the cartesian coordinates Fukui Index S70

71 S71

72 Figure S44. Partial NBO charge distributions in intermediate C calculated at the B3LYP/6-311G(d) level. S72

73 Table S7. NBO charge distributions for C 70 carbon cage in intermediate C calculated at the B3LYP/6-311G(d) level. Atomic number in Figure Atomic number in the cartesian Charge S43 coordinates S73

74 S74

75 Optimized structure, cartesian coordinates and the lowest frequency for 7,23-Bn 2 C 70 obtained at B3LYP/6-31G level. Geometry for 7,23-Bn 2 C 70 Charge = 0 Multiplicity = 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S75

76 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H C S76

77 C H C H C H C H C H C H H C C H C H C H C H C H Lowest frequency = cm 1 S77

78 Optimized structure, cartesian coordinates, the lowest frequency and sum of electronic and zero-point energies for intermediate A obtained at B3LYP/6-31G level. Geometry for intermediate A Charge = -1 Multiplicity = 1 O C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S78

79 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H S79

80 C C H C H C H C H C H C H H C C H C H C H C H C H C H H H Lowest frequency = cm 1 Sum of electronic and zero-point energies = hartree (1 hartree = kcal/mol) S80

81 Optimized structure, cartesian coordinates, the lowest frequency and sum of electronic and zero-point energies for the isomer of intermediate A obtained at B3LYP/6-31G level. Geometry for the isomer of intermediate A Charge = -1 Multiplicity = 1 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S81

82 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H S82

83 C C H C H C H C H C H C H H C C H C H C H C H C H O C H H H Lowest frequency = cm 1 Sum of electronic and zero-point energies = hartree (1 hartree = kcal/mol) S83

84 Optimized structure, cartesian coordinates and the lowest frequency for 1,4-Bn 2-11-MeOC 60 obtained at B3LYP/6-31G level Geometry for intermediate 1,4-Bn 2-11-MeOC 60 Charge = -1 Multiplicity = 1 C C C C C C C C C C C C C C C H H C C C C C C C C C C C C C S84

85 C H H C C C C C C C C C H C C H C C C C C C C C C C C C H C H C C H C C H C C C C C C H S85

86 C C H C H C C C C C C H C C O C H H H Lowest frequency = 18.44cm 1 S86

87 Optimized structure, cartesian coordinates and the lowest frequency for intermediate B obtained at B3LYP/6-31G level. Geometry for intermediate B Charge = -2 Multiplicity = 1 O C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S87

88 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H S88

89 C C H C H C H C H C H C H H C C H C H C H C H C H C H H H O C H H H Lowest frequency = cm 1 S89

90 Optimized structure, cartesian coordinates and the lowest frequency for 2a obtained at B3LYP/6-31G level. Geometry for 2a Charge = 0 Multiplicity = 1 Br Br O O C C C C C C C C C C C C C C C C C C C C C C S90

91 C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C S91

92 C C C C C H H C C H C H C H C H C C H H C H H C C C H C H C H C H C H H C H H C C H C H S92

93 C H C H C H C H H C C H C H C H C H C H C H H H C H H H Lowest frequency = cm 1 S93

94 Optimized structure, cartesian coordinates and the lowest frequency for intermediate C obtained at B3LYP/6-31G level. Geometry for intermediate C Charge = -1 Multiplicity = 1 Br Br O O C O C C C C C C C C C C C C C C C C C C C C C C C S94