1S

Tethered Bis-pyrrolidine Additions to C70: Some

Unexpected and New Regioisomers

Maira R. Cerón,a‡ Marta Izquierdo,a‡ Amineh Aghabali,b‡ Sophie P. Vogel,a Marilyn M.

Olmstead,*b Alan L. Balch,* b Luis Echegoyen*a

a Department of Chemistry, University of Texas at El Paso, 500W University Ave, El Paso, TX

79968 (USA)

b Department of Chemistry, University of California at Davis, One Shields Ave, Davis, CA 95616

(USA)

SUPPORTING INFORMATION

Contents

General methodology and synthesis of compounds 1-4 2S

HPLC profile of the mixture of bis-adducts 2S

Mass spectra of compounds 1-4 3S

UV-vis spectra of compounds 1-4 in toluene 4S

1H-NMR spectra of compound 1 5S

COSY-NMR spectra of compound 1 6S

13C-NMR spectra of compound 1 6S

1H-NMR spectra of compound 2 7S

COSY-NMR spectra of compound 2 7S

13C-NMR spectra of compound 2 8S

Cyclic Voltammetry of compound 1 and compound 2 8S

HPLC profile of isomerization of compound 1 and 2 9S

Recycling HPLC of compounds 3 and 4 9S

1H-NMR spectra of compound-3 10S

COSY-NMR spectra of compound-3 10S

1H-NMR spectra of compound-4 11S

COSY-NMR spectra of compound-4 11S

2S

General Methodology

All chemicals were of reagent grade, purchased from Sigma Aldrich. Silica gel (Redisep silica, 40-

60 µ, 60 Å) was used to purify the products, also Silica gel Prep TLC Plates, w/UV254, glass

backed, 20 x 20 cm, 1000 μm. MALDI-TOF mass spectrometry was conducted on a Bruker

Microflex LRF mass spectrometer, positive mode, samples dissolved in carbon disulfide, matrix

THA and TPB. NMR spectra were recorded using a JEOL 600 MHz spectrometer. The UV-vis-

NIR spectra were taken using a Cary 5000 UV-vis-NIR spectrophotometer. The FT-IR spectra

were taken using a Bruker Tensor 27 spectrophotometer.

Cyclic voltammetry (CV) and square wave voltammetry (SWV) experiments were carried out

under an Argon atmosphere at room temperature using a CH Instrument Potentiostat. Scan rate for

CV experiments was 100 mV/s. For the SWV experiments, scan rate of 100 mV/s with increments

of 4 mV, amplitude of 25 mV and frequency of 15 Hz were used. A one compartment cell with a

standard three-electrodes set up was used, consisting of a 1 mm diameter glassy carbon disk as the

working electrode, a platinum wire as counter electrode and a silver wire as pseudo-reference

electrode, with a solution of anhydrous o-DCB containing 0.05 M n-Bu4NPF6. Ferrocene was

added to the solution at the end of each experiment as internal standard. The X-ray intensity data

were measured on a Bruker SMART APEX CCD system equipped with a graphite monochromator

and a MoKα fine-focus tube (λ = 0.71073 Å).

Synthesis of bispyrrolidino [70]fullerene

Figure S1. HPLC profile of the mixture of bis-adducts after removing unreacted C70. (Conditions:

5-PBB column (4.6 ID x 250 mm); toluene (1.2 mLmin-1) at room temperature; λ = 320 nm).

3S

Figure S2. MALDI-TOF spectrum of compound 1 using 1,1,4,4-tetraphenyl-1,3-butadiene (TPB)

as matrix.

Figure S3. MALDI-TOF spectrum of compound 2 using TPB as matrix.

Figure S4. MALDI-TOF spectrum of compound 3 using 1,8,9-trihydroxyanthracene (THA) as

matrix.

4S

Figure S5. MALDI-TOF spectrum of compound 4 using THA as matrix.

Figure S6. UV/Vis spectra of compounds 1, 2, 3 and 4 in toluene.

5S

Figure S7. UV/Vis spectra comparison of compound 1, 2, 3, 4, bis-adduct-4 and bis-adduct-5 (see

reference 1 for structures).i

Figure S8. 1H-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K); compound 1: δ 7.35 (dd, 1HAr, J = 3.61,

5.64), 7.07 (dd, 1HAr, J = 3.49, 5.77), 4.60 (d, 1H, J = 10.19), 4.21 (s, 1H), 3.68 (d, 1H, J = 10.22),

3.37 (m, 1H, N-CH2-CH3, J = 7.56, 12.48), 2.35 (m, 1H, N-CH2-CH3, J = 6.91, 13.87), 1.39 (t, 1H,

N-CH2-CH3, J = 7.24) ppm.

6S

Figure S9. COSY-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K) of compound 1.

Figure S10. 13C-NMR (150 MHz; CDCl3/CS2 (7/3), 298 K); compound 1: δ 14.19, 49.77, 58.91,

59.65, 65.55, 79.25, 120.94, 126.51, 127.36, 127.38, 137.34, 138.56, 140.58, 143.27, 143.96,

145.00, 146.65, 148.54, 149.70, 149.78, 150.70, 150.89, 156.80, 158.03 ppm.

7S

Figure S11. 1H-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K); compound 2: δ 7.89 (dd, 1HAr, J =

3.71, 5.47), 7.54 (dd, 1HAr, J = 3.44, 5.67), 4.74 (d, 1H, J = 9.92), 4.10 (s, 1H), 3.60 (m, 1H, N-

CH2-CH3, J = 7.38, 14.90), 3.40 (d, 1H, J = 9.85), 2.38 (m, 1H, N-CH2-CH3, J = 6.96, 13.90), 1.53

(t, 1H, N-CH2-CH3, J = 7.22) ppm.

Figure S12. COSY-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K) of compound 2.

8S

Figure S13. 13C-NMR (150 MHz; CDCl3/CS2 (7/3), 298 K); compound 2: δ 14.36, 49.77, 59.49,

61.66, 64.57, 80.95, 127.31, 128.12, 132.62, 133.22, 134.22, 135.00, 135.52, 138.63, 138.79,

139.98, 141.76, 142.02, 142.25, 144.01, 144.93, 146.21, 148.38, 148.40, 148.67, 148.90, 149.58,

149.67, 150.05, 150.09, 151.12, 152.32, 158.73, 159.07 ppm.

Figure S14. Cyclic voltammetry of compound 1 and compound 2 (o-DCB containing 0.05 M n-

Bu4NPF6; using the redox couple Fc/Fc+ as internal reference).

9S

Figure S15. HPLC profile of compound 1 and compound 2 (Conditions: 5-PBB column (4.6 ID x

250 mm); toluene (1.2 mLmin-1) at room temperature; λ = 320 nm). After heating at o-DCB reflux

a) 0 h; b) 1 h; c) 2 h; d) 5 h; e) 7 h.

Figure S16. Recycling HPLC of the mixture of compounds 3 and 4 (Conditions: Buckyprep

column (10 ID x 250 mm); toluene (4 mLmin-1) at room temperature; λ = 320 nm).

10S

Figure S17. 1H-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K); compound 3: δ 7.48 (d, 1HAr, J =

7.51), 7.34 (t, 1HAr, J = 7.43), 7.10 (t, 1HAr, J = 7.53), 7.00 (d, 1HAr, J = 7.49), 5.92 (s, 1H), 4.82

(d, 1H, J = 8.37), 4.25 (d, 1H, J = 9.89), 3.72 (m, 1H, N-CH2-CH3), 3.72 (s, 1H), 3.28 (d, 1H, J =

8.37), 3.13 (d, 1H, J = 9.83), 2.80 (m, 1H, N-CH2-CH3), 2.45 (m, 1H, N-CH2-CH3), 2.22 (m, 1H,

N-CH2-CH3), 1.50 (t, 1H, N-CH2-CH3, J = 7.19), 1.12 (t, 1H, N-CH2-CH3, J = 7.18) ppm.

Figure S18. COSY-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K) of compound 3.

11S

Figure S19. 1H-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K); compound 4: δ 7.64 (d, 1HAr, J =

7.39), 7.58 (t, 1HAr, J = 7.48), 7.55 (t, 1HAr, J = 7.34), 7.44 (d, 1HAr, J = 7.02), 5.71 (s, 1H), 4.28

(d, 1H, J = 8.54), 4.21 (s, 1H), 4.14 (d, 1H, J = 9.29), 3.70 (m, 1H, N-CH2-CH3), 3.35 (d, 1H, J =

9.27), 2.95 (d, 1H, J = 8.53), 2.95 (m, 1H, N-CH2-CH3), 2.38 (m, 1H, N-CH2-CH3), 1.36 (t, 1H, N-

CH2-CH3, J = 7.16), 1.14 (t, 1H, N-CH2-CH3, J = 7.24) ppm.

Figure S20. COSY-NMR (600 MHz; CDCl3/CS2 (7/3), 298 K) of compound 4.

12S

All Density Functional Theory (DFT) calculations have been performed with the Gaussian-09

code[ii] using the B3LYP functional and the 6-311G* basis set respectively.

Figure S21. Optimized structures of possible stereo-conformations of α-2-α.

i Cerón, M. R.; Izquierdo, M.; Aghabali, A.; Valdez, J. A.; Ghiassi, K. B.; Olmstead, M. M.; Balch, A. L.; Wudl, F.; Echegoyen, L. J. Am. Chem. Soc. 2013, 137, 7502. ii Gaussian 09, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian, Inc, Wallingford CT, 2009.