Supplementary Information
One-dimensional Polar Assembly of Fullerene Nano-shuttlecocks
in Crystals and Liquid Crystals
Masaya Sawamura*,‡, Kenji Kawai*, Yutaka Matsuo*, Kiyoshi Kanie†,
Takashi Kato†& Eiichi Nakamura*
*Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
†Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
‡Present address: Department of Chemistry, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan
Table of Contents
1. Synthetic Procedures
2. Optical Texture of Thermotropic LC of 2
3. SAXD d-Spacings for Thermotropic LC of 2
4. Wide angle X-ray Diffraction Data for Thermotropic LC of 2
5. SAXD Data for Lyotropic LC of 2
6. SAXD d-Spacings for the Lyotropic LC of 2
7. References
1. Synthetic Procedures
1,4,11,15,30-Pentakis(biphenyl)-2H-1,2,4,11,15,30-hexahydro[60]fullerene(1).This compound was prepared according to the published procedure1.To a suspension of CuBr•SMe2(11.4 g, 55.4 mmol) in THF (60 mL) was added a 1.0 M solution of 4-(C6H5)C6H4MgBr (27.8 mmol) in THF (27.8 ml) under N2. The resulting yellow suspension was stirred for 10 min. After addition of a solution of C60(1.00 g, 1.39 mmol) in 1,2-dichlorobenzene (90mL), the reaction mixture was stirred for 2h at 20 ℃. The reaction was stopped by addition of NH4Cl(aq) (4 mL). After dilution with toluene (200 mL), the mixture was filtered through a pad of silica gel. Most of volatile materials were removed under reduced pressure with a rotary evaporator to obtain a concentrated solution. Upon addition of Et2O, precipitates formed and were collected. The powder was washed with Et2O. The resulting orange solid was dried in vacuo to obtainthe title compound (2.05 g, 99.1% yield):1H NMR (400 MHz, CDCl3/CS2 = 4/1)7.89 (d, J = 0.84 Hz, 4H, aromatic CH), 7.71 (d, J = 0.84 Hz, 4H, aromatic CH), 7.64 (d, J = 0.2 Hz, 2H, aromatic CH), 7.56-7.25 (m, 35H, aromatic CH),5.40 (s, 1H, C60H); 13C NMR (100 MHz, CDCl3/CS2 = 4/1)155.69, 152.29, 151.83, 151.10, 148.48, 148.43, 148.40, 148.11, 147.98, 147.81, 147.47, 147.38, 146.88, 146.79, 146.60, 145.73, 145.53, 145.33, 145.05, 144.21, 144.16, 144.14, 144.06, 143.96, 143.88, 143.39, 142.98, 140.36, 139.94, 139.90, 139.87, 139.77, 138.31, 138.29, 128.58, 128.51, 128.48, 128.33, 128.17, 127.88, 127.30, 127.26, 127.24, 127.16, 127.07, 127.02, 126.77, 126.73, 127.70, 62.94, 60.61, 58.61, 58.50. Anal. Calcd for C120H45•C6H5Cl: C, 94.57; H, 3.21. Found: C, 94.68; H, 3.07.
1,4,11,15,30-Pentakis(4-hydroxyphenyl)-2H-1,2,4,11,15,30-hexahydro-[60]fullerene. To a suspension of CuBr·SMe2(11.4 g, 55.4 mmol) in THF (170 ml) was added a solution of 4-THPOC6H4MgBr in THF (55.5 mL, 55.5 mmol) under N2. The resulting dark-red solution was stirred for 10 min. After addition of a solution of C60(2.00 g, 2.78 mmol) in 1,2-dichlorobenzene(150 mL), the reaction mixture was stirred for 2h at 23 ℃. The reaction was stopped by addition of NH4Cl(aq) (4 mL). After dilution with toluene (400 mL), the mixture was filtered through a pad of silica gel. Most of volatile materials were removed under reduced pressure with a rotary evaporator to obtain a concentrated solution. After addition of EtOH, precipitates formed and were collected. The powder was washed with EtOH to obtain an orange solid, which was dried in vacuo. This orange solid was dissolved in CH2Cl2/MeOH (300 mL, 50% v/v), and TsOH·H2O (145 mg, 0.762 mmol) was added to the solution. After the mixture was stirred for 1day, it was neutralized with NaHCO3. Insoluble products were removed by filtration with a pad ofCelite. Solvent was evaporated, and the residue was dissolved with a small amount of EtOH. Upon addition of hexane, orange powder precipitated. The precipitates were collected and washed with hexane, and then dried in vacuo to obtain title compound, (4-HOC6H4)5HC60 (3.04 g, 92.1% yield): 1H NMR (400 MHz, acetone-d6)8.49 (s, 2H, OH), 8.38 (s, 2H, OH), 7.75 (d, J = 8.4 Hz, 4H, aromaticCH), 7.56 (d, J = 8.8 Hz, 4H, aromaticCH), 7.26 (d, J = 8.4 Hz, 2H, aromaticCH), 6.87 (d, J = 8.4 Hz, 4H, aromaticCH),6.72 (d, J = 8.8 Hz, 4H, aromaticCH), 6.64 (d, J = 8.4 Hz, 2H, aromaticCH), 5.45 (s, 1H, C60H); 13C NMR (100 MHz, acetone-d6)157.63, 157.49, 157.38, 157.08, 153.60, 152.92, 149.11, 149.09, 149.03, 148.83, 148.66, 148.50, 148.47, 148.14, 147.70, 147.60, 147.50, 147.38, 146.75, 146.58, 146.29, 145.41, 144.81, 144.76, 144.71, 144.69, 144.54, 144.44, 143.56, 137.41, 130.85, 130.77, 130.00, 129.93, 129.54, 116.42, 116.12, 116.04, 64.00, 63.61, 61.29, 59.28.
1,4,11,15,30-Pentakis{4-[3,4-di(dodecan-1-yloxy)benzoyloxy]phenyl}-2H-1,2,11,15,30-pentahydro[60]fullerene (2). To a mixture of (4-HOC6H4)5HC60 (302mg, 0.254 mmol) and 3,4-di(dodecan-1-yloxy)benzoyl chloride (820mg, 1.61 mmol)in THF (30 mL) was added triethylamine(0.250 mL, 1.79 mmol) and 4-dimethylaminopyridine (154.6mg, 1.27 mmol). After the reaction mixture was stirred for 3 h,a solution was quenched with 10 % HCl(aq).The product was extractedwithchloroform (40 mL). The organic layer was washed with 10 % HCl(aq) (50 mL) and sat. NaCl(aq) (50 mL), and then dried over MgSO4. After filtration, solvent was evaporated. Purification by silica gel column chromatography (CHCl3) and GPC (Japan Analytical Industry Co. Ltd. Jaigel 2Hand 3H, eluent: toluene) was carried out. Reprecipitation from MeOH/toluene afforded 2 (684 mg, 75.8% yield): IR (film), 1745cm-1 (s, C=O); 1H NMR (CDCl3, 400 MHz)7.87 (d, J = 8.8 Hz, 4H, C6H4), 7.79 (m, 5H, C6H3), 7.69 (d, J = 8.8 Hz, 4H, C6H4), 7.64 (m, 5H, C6H3), 7.52 (d, J = 8.8 Hz, 2H, C6H4), 7.23 (d, J = 8.8 Hz, 4H, C6H4), 7.12 (d, J = 8.8 Hz, 4H, C6H4), 7.09 (d, J = 8.8 Hz, 2H, C6H4), 6.90 (m, 5H, C6H3),5.40 (s, 1H, C60H), 4.05 (t, J = 6.6 Hz, 10H, OCH2), 4.04 (t, J = 6.6 Hz, 10H, OCH2), 1.84 (br, 20H, OCH2CH2), 1.48 (br, 20H, OCH2CH2CH2), 1.25 (br, 160H, O(CH2)3(CH2)8CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3);13C NMR (CDCl3, 100MHz)164.72, 164.67, 164.64, 155.72, 153.70, 153.65, 152.55, 151.89, 151.27, 150.52, 150.16, 148.70, 148.66, 148.59, 148.53, 148.51, 148.49, 148.32, 148.19, 148.02, 147.67, 147.44, 147.10, 147.01, 145.68, 145.65, 145.42, 145.11, 144.37, 144.31, 144.22, 144.17, 144.12, 144.02, 143.46, 143.13, 142.72, 136.85, 136.80, 129.09, 128.92, 128.70, 124.36, 124.33, 122.36, 122.26, 122.13, 121.40, 121.33, 121.27, 114.54, 114.50, 111.81, 111.78, 69.38, 69.07, 60.57, 58.61, 58.50, 32.01, 29.78, 29.75, 29.70, 29.52, 29.49, 29.45, 29.30, 29.18, 26.15, 26.09, 22.79, 14.22. ESI-MS (toluene/acetonitrile = 1/9): m/z = 3549. Anal. Calcd for C245H286O20: C, 82.47; H, 7.93. Found: C, 82.26; H, 8.00.
1,4,11,15,30-Pentakis{4-[3,4-di(tetradecan-1-yloxy)benzoyloxy]phenyl}-2H-1,2,4,11,15,30-hexahydro[60]fullerene (3). Compound 3 was synthesized by the same procedure described for the synthesis of 2. The reaction using (4-HOC6H4)5HC60 (103 mg, 0.0867 mmol), 3,4-di(tetradecan-1-yloxy)benzoyl chloride (347 mg, 0.613 mmol), triethyleneamine (0.100 ml, 0.717 mmol), and 4-dimethylaminopyridine (51.3 mg, 0.420 mmol) in THF (30 mL) afforded 3 (218 mg, 65.6% yield): IR (film), 1743 cm-1 (s, C=O); 1H NMR (CDCl3, 400 MHz) 7.87 (d, J = 8.8 Hz, 4H, C6H4), 7.79 (m, 5H, C6H3), 7.69 (d, J = 8.8 Hz, 4H, C6H4), 7.64 (m, 5H, C6H3), 7.52 (d, J = 8.8 Hz, 2H, C6H4), 7.23 (d, J = 8.8 Hz, 4H, C6H4), 7.12 (d, J = 8.8 Hz, 4H, C6H4), 7.09 (d, J = 8.8 Hz, 2H, C6H4), 6.90 (m, 5H, C6H3),5.40 (s, 1H, C60H), 4.05 (t, J = 6.6 Hz, 10H, OCH2), 4.04 (t, J = 6.6 Hz, 10H, OCH2), 1.84 (br, 20H, OCH2CH2), 1.48 (br, 20H, OCH2CH2CH2), 1.25 (br, 200H, O(CH2)3(CH2)10CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3);13C NMR (100 MHz, CDCl3) 164.57, 164.53, 164.50, 155.58, 153.56, 153.51, 152.41, 151.75, 151.13, 150.54, 150.38, 150.02, 148.56, 148.51, 148.46, 148.40, 148.37, 148.36, 148.18, 148.05, 147.89, 147.30, 146.96, 146.88, 146.69, 145.54, 145.28, 144.97, 144.23, 144.17, 144.08, 144.03, 143.98, 143.88, 143.32, 143.00, 136.71, 136.66, 128.95, 128.79, 128.56, 124.19, 122.23, 122.12, 122.00, 121.27, 121.20, 121.13, 114.39, 111.63, 69.24, 68.93, 60.43, 58.48, 58.36, 31.88, 29.67, 29.62, 29.58, 29.40, 29.37, 29.32, 29.17, 29.05, 28.96, 26.02, 25.96, 22.66, 14.10.ESI-MS (toluene/acetonitrile = 1/9): m/z = 3829. Anal. Calcd for C265H326O20: C, 83.07; H, 8.58. Found: C, 82.94; H, 8.56.
1,4,11,15,30-Pentakis{4-[3,4-di(hexadecan-1-yloxy)benzoyloxy]phenyl}-2H-1,2,4,11,15-hexahydro[60]fullerene (4).Compound 4 was synthesized by the same procedure described for the synthesis of 2. The reaction using (4-HOC6H4)5HC60 (79.6mg, 0.0671 mmol), 3,4-di(hexadecan-1-yloxy)benzoyl chloride (296 mg, 0.477 mmol), triethylamine (73L, 0.52 mmol), and 4-dimethylaminopyridine (42.6 mg, 0.349 mmol) in THF (30 mL) afforded 4 (216 mg, 78.4% yield): IR (film), 1743 cm-1 (s, C=O); 1H NMR (CDCl3, 400 MHz)7.87 (d, J = 8.8 Hz, 4H, C6H4), 7.79 (m, 5H, C6H3), 7.69 (d, J = 8.8 Hz, 4H, C6H4), 7.64 (m, 5H, C6H3), 7.52 (d, J = 8.8 Hz, 2H, C6H4), 7.23 (d, J = 8.8 Hz, 4H, C6H4), 7.12 (d, J = 8.8 Hz, 4H, C6H4), 7.09 (d, J = 8.8 Hz, 2H, C6H4), 6.90 (m, 5H, C6H3),5.40 (s, 1H, C60H), 4.05 (t, J = 6.6 Hz, 10H, OCH2), 4.04 (t, J = 6.6 Hz, 10H, OCH2), 1.84 (br, 20H, OCH2CH2), 1.48 (br, 20H, OCH2CH2CH2), 1.25 (br, 240H, O(CH2)3(CH2)12CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3);13C NMR (100 MHz, CDCl3)164.58, 164.54, 164.50, 155.58, 153.57, 153.52, 152.41, 151.75, 151.13, 150.54, 150.38, 150.02, 148.56, 148.52, 148.46, 148.42, 148.40, 148.37, 148.18, 148.05, 147.89, 147.30, 146.97, 146.88, 146.69, 145.54, 145.27, 144.97, 144.23, 144.17, 144.08, 144.03, 143.98, 143.88, 143.32, 143.00, 136.71, 136.66, 128.94, 128.79, 128.56, 124.22, 122.19, 122.13, 122.00, 121.27, 121.20, 121.13, 114.40, 114.36, 111.66, 111.64, 69.24, 68.94, 60.43, 58.47, 58.35, 31.88, 29.67, 29.62, 29.59, 29.41, 29.38, 29.32, 29.18, 29.06, 28.96, 26.03, 25.97, 22.66, 14.10. Anal. calcd for C285H366O20: C, 83.25; H, 8.97. Found: C, 83.01; H, 8.94.
1, 4, 11, 15, 30-Pentakis{4-[3,4-di(octadecan-1-yloxy)benzoyloxy]phenyl}-2H-1, 4, 11, 15, 30-hexahydro[60]fullerene (5). Compound 5 was synthesized by the same procedure described for the synthesis of 2. The reaction using (4-HOC6H4)5HC60 (78.9 mg, 0.0665 mmol), 3,4-di(octadecan-1-yloxy)benzoyl chloride (300 mg, 0.465 mmol), triethylamine(0.0750 ml, 0.538 mmol), and 4-dimethylaminopyridine (44.0 mg, 0.360 mmol) in THF (30 mL) afforded 5 (215 mg, 73.7% yield): IR (film), 1745 cm-1 (s, C=O); 1H NMR (CDCl3, 400 MHz):7.87 (d, J = 8.8 Hz, 4H, C6H4), 7.79 (m, 5H, C6H3), 7.69 (d, J = 8.8 Hz, 4H, C6H4), 7.64 (m, 5H, C6H3), 7.52 (d, J = 8.8 Hz, 2H, C6H4), 7.23 (d, J = 8.8 Hz, 4H, C6H4), 7.12 (d, J = 8.8 Hz, 4H, C6H4), 7.09 (d, J = 8.8 Hz, 2H, C6H4), 6.90 (m, 5H, C6H3),5.40 (s, 1H, C60H), 4.05 (t, J = 6.6 Hz, 10H, OCH2), 4.04 (t, J = 6.6 Hz, 10H, OCH2), 1.84 (br, 20H, OCH2CH2), 1.48 (br, 20H, OCH2CH2CH2), 1.25 (br, 280H, O(CH2)3(CH2)14CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3), 0.87 (t, J = 6.6 Hz, 15H, CH3); 13C NMR (100 MHz, CDCl3)164.57, 164.52, 164.50, 155.57, 153.54, 153.49, 152.40, 151.74, 151.12, 150.53, 150.38, 150.01, 148.56, 148.51, 148.45, 148.38, 148.36, 148.34, 148.17, 148.04, 147.88, 147.29, 146.96, 146.86, 146.68, 145.53, 145.27, 144.97, 144.22, 144.16, 144.07, 144.02, 143.97, 143.87, 143.31, 142.99, 136.70, 136.65, 128.94, 128.78, 128.55, 124.19, 122.23, 122.12, 121.99, 121.25, 121.18, 121.12, 114.36, 111.60, 69.23, 68.92, 60.43, 58.47, 58.35, 31.88, 29.68, 29.62, 29.60, 29.42, 29.39, 29.32, 29.18, 29.05, 28.98, 26.03, 25.97, 22.66, 14.10.Anal. Calcd for C305H406O20: C, 83.40; H, 9.32. Found: C, 83.24; H, 9.32.
2. Optical Textures of Thermotropic LC of 2
(a)
(b)
Figure S1. Optical polarized micrographs of thermotropic LC of 2. (a) Optical texture of thermotropic LC of 2 observed at 110 ºC on the first heating. (b) Optical texture observed on annealing for 2 h at 110 ºC.
3. SAXD d-Spacings for the Thermotropic LC of 2
Table S1. SAXD d-spacings for the thermotropic LC of 2 at various temperatures.
———————————————————————————————
T (ºC)2 (º)d (Å)hkld(100)> aa (Å) b
———————————————————————————————
602.8131.4100 30.635.3
5.2516.8110
5.6515.6200
6.1514.3001
802.8331.1100 30.535.3
5.2316.9110
5.6515.6200
6.0714.5001
100 2.8431.1100 30.635.4
5.2116.9110
5.6515.6200
6.0714.5001
120 2.8431.1100 30.635.4
5.1917.0110
5.6515.6200
6.0514.6001
140 2.8431.1100 30.635.4
5.1917.0110
5.6515.6200
6.0514.6001
———————————————————————————————
a <d100> = (d100 + 31/2d110 + 41/2d200)/3. b Column diameter a = 2<d100>/31/2.
4. Wide angle X-ray Diffraction Data for the Thermotropic LC of 2
Figure S2.Wide angle X-ray diffraction pattern for the thermotropic LC of 2 at 25 ºC.
5. SAXD Data for Lyotropic LC of 2
Figure S3.Detail patterns of SAXD data of the lyotropic LC of 2 at various temperatures. (a) The SAXD data of the 0- to 10-deg region at 60-90 °C.(b) Enlarged patterns of the 4.5- to 6-deg region at 60-90 °C. For the data at 60 °C, d(100) = 34.4 Å, d(110) = 19.9 Å, d(001) = 17.5 Å, d(200) = 17.3 Å.
6. SAXD d-Spacings for the Lyotropic LC of 2
Table S2. SAXD d-spacings for the thermotropic LC of 2 at various temperatures.
—————————————————————————————————
T (ºC) 2(º)d (Å)hkld(100)> (Å)aa (Å)bLC phase
—————————————————————————————————
602.5734.410034.539.8Colh
4.4319.9110
5.0517.5001
5.1117.3200
702.5834.310034.239.5Colh
4.5019.7110
5.0017.7001
5.1117.3200
802.5934.110034.239.5Colh
4.4220.0110
5.0017.4001
5.1917.0200
902.6034.010034.139.4Colh
4.4619.8110
4.9817.8001
5.1917.0200
1.1874.6––74.6Ncol
1001.5756.3––56.3Ncol
—————————————————————————————————
a <d100> = (d100 + 31/2d110 + 41/2d200)/3. b Column diameter a = 2<d100>/31/2.
7. References
1. Sawamura, M., Iikura, H., Ohama, T., Hackler, U. E., & Nakamura, E. Single-step synthesis of pentaaryl-monohydro[60]fullerenes through fivefold addition of organocopper reagent to C60. J. Organomet. Chem. 599, 32-36 (2000).
1