Supporting Information. Yu-Wu Zhong, Yutaka Matsuo,* and Eiichi Nakamura*
|
|
- Lindsey Fox
- 5 years ago
- Views:
Transcription
1 Supporting Information Lamellar Assembly of Conical Molecules Possessing a Fullerene Apex in Crystals and Liquid Crystals Yu-Wu Zhong, Yutaka Matsuo,* and Eiichi Nakamura* Nakamura Functional Carbon Cluster Project, ERATO, Japan Science and Technology Agency (JST), The University of Tokyo, Hongo, Bunkyo-ku, Tokyo , Japan matsuo@chem.s.u-tokyo.ac.jp; nakamura@chem.s.u-tokyo.ac.jp Table of Contents 1. Synthetic Procedures 2. Single Crystal X-ray Crystallographic Analysis of 1 and 2 3. Optical Textures of Liquid Crystals 4. DSC Measurement of Liquid Crystals 5. X-ray Diffraction Data for Liquid Crystals S1
2 1. Synthetic Procedures General. All experiments were carried out under argon using standard Schlenk techniques. THF was distilled from Na/K alloy, and dichloromethane was distilled from CaH 2 before use. 4-BrC 6 H 4 C CSiMe 3, n C 4 H 9 SiMe 2 Cl, n C 8 H 17 SiMe 2 Cl, n C 10 H 21 SiMe 2 Cl, and n C 12 H 25 SiMe 2 Cl were commercially available and used as received. n C 14 H 29 SiMe 2 Cl was prepared according to literature. 1 All 1 H (500 MHz) and 13 C{ 1 H} (125 MHz) spectra were recorded on JEOL ECA500 spectrometers. Spectra were reported in parts per million from internal tetramethylsilane (δ 0.00 ppm) or residual protons of the deuterated solvent for 1 H NMR, from solvent carbon (e.g. δ ppm for chloroform) for 13 C{ 1 H} NMR. HPLC analyses were performed on Shimadzu LC-10A system equipped with SPD-M10A diode array detector and Cosmosil-Buckyprep column (4.6 x 250 mm, Nacalai Tesque Co.). Preparative HPLC separations were performed by the use of a Buckyprep column (20 mm x 250 mm) using toluene/2-propanol (6/4) as eluent. High-resolution mass spectra were measured on a JEOL JMS-T100LC ESI-TOF mass spectrometer. IR spectra were recorded on Applied Systems Inc. React-IR A General Procedure for the Preparation of 4-BrC 6 H 4 C CSiMe n 2 C n H 2n+1. To a solution of 1-bromo-4-ethylnylbenzene (362 mg, 2.0 mmol) in 10 ml of THF was added dropwise a solution of i-prmgbr (2.1 mmol) in THF (3.1 ml, 0.67 M) at 0 C. The mixture was stirred for 20 min before the ice bath was removed. Stirring was continued for another 10 min at room temperature, followed by the addition of 2.5 mmol of corresponding n-c n H 2n+1 SiMe 2 Cl. Two hours later, the reaction was quenched by 5.0 ml of saturated aqueous ammonium chloride solution. After extraction with ethyl acetate, the combined organic phase was concentrated and subjected to flash column chromatography to afford the desired product. Br iprmgbr THF C n H 2n+1 SiMe 2 Cl Br SiMe 2 C n H 2n+1 n = 4, 8, 10, 12, 14 1-(4-Bromophenylethynyl)- n butyl-dimethylsilane [4-Br-C 6 H 4 C CSiMe 2 (n-c 4 H 9 )]. 1 H NMR (CDCl 3 ): δ 0.21 (s, 6H, SiMe 2 ), 0.68 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.91 (t, J = 1 Itami, K.; Terakawa, K.; Yoshida, J.-I.; Kajimoto, O. J. Am. Chem. Soc. 2003, 125, S2
3 6.90 Hz, 3H, CH 2 CH 3 ), (m, 4H, 2CH 2 ), 7.32 (d, J = 8.60 Hz, 2H, ArH), 7.42 (d, J = 8.60 Hz, 2H, ArH). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (SiCH 2 ), (CH 2 CH 3 ), (CH 2 ), (CH 2 ), (C CSi), (C CSi), (1C, Ar), (1C, Ar), (2C, Ar), (2C, Ar). 1-(4-Bromophenylethynyl)-dimethyl- n octylsilane [4-Br-C 6 H 4 C CSiMe 2 (n-c 8 H 17 )]. 1 H NMR (CDCl 3 ): δ 0.22 (s, 6H, SiMe 2 ), 0.69 (t, J = 8.10 Hz, 2H, SiCH 2 ), 0.89 (t, J = 6.90 Hz, 3H, CH 2 CH 3 ), (m, 12H, 6CH 2 ), 7.32 (d, J = 8.60 Hz, 2H, ArH), 7.42 (d, J = 8.00 Hz, 2H, ArH). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (SiCH 2 ), (CH 2 CH 3 ), (CH 2 ), 23.79(CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (C CSi), (C CSi), (1C, Ar), (1C, Ar), (2C, Ar), (2C, Ar). 1-(4-Bromophenylethynyl)-dimethyl- n decylsilane [4-Br-C 6 H 4 C CSiMe 2 (n-c 10 H 21 )]. 1 H NMR (CDCl 3 ): δ 0.21 (s, 6H, SiMe 2 ), 0.68 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.88 (t, J = 6.90 Hz, 3H, CH 2 CH 3 ), (m, 16H, 8CH 2 ), 7.31 (d, J = 8.55 Hz, 2H, ArH), 7.42 (d, J = 8.60 Hz, 2H, ArH). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (SiCH 2 ), (CH 2 CH 3 ), (CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (CH 2 ), (C CSi), (C CSi), (1C, Ar), (1C, Ar), (2C, Ar), (2C, Ar). 1-(4-Bromophenylethynyl)-dimethyl- n dodecylsilane [4-Br-C 6 H 4 C CSiMe 2 (n-c 12 H 25 )]. 1 H NMR (CDCl 3 ): δ 0.21 (s, 6H, SiMe 2 ), 0.68 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.88 (t, J = 6.90 Hz, 3H, CH 2 CH 3 ), (m, 20H, 10CH 2 ), 7.32 (d, J = 8.60 Hz, 2H, ArH), 7.42 (d, J = 8.60 Hz, 2H, ArH). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (1C, SiCH 2 ), (1C, CH 2 CH 3 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (2C, 2CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (C CSi), (C CSi), (1C, Ar), (1C, Ar), (2C, Ar), (2C, Ar). 1-(4-Bromophenylethynyl)-dimethyl- n tetradecylsilane [4-Br-C 6 H 4 C CSiMe 2 (n-c 14 H 29 )]. 1 H NMR (CDCl 3 ): δ 0.22 (s, 6H, SiMe 2 ), 0.68 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.89 (t, J = 6.90 Hz, 3H, CH 2 CH 3 ), (m, 24H, 12CH 2 ), 7.32 (d, J = 8.60 Hz, 2H, ArH), 7.43 (d, J = 8.05 Hz, 2H, ArH). 13 C NMR (CDCl 3 ): δ S3
4 -1.78 (2C, SiMe 2 ), (1C, SiCH 2 ), (1C, CH 2 CH 3 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (2C, 2CH 2 ), (2C, 2CH 2 ), (2C, 2CH 2 ), (1C, CH 2 ), (1C, CH 2 ), (C CSi), (C CSi), (1C, Ar), (1C, Ar), (2C, Ar), (2C, Ar). (4-Bromophenylethynyl)-dimethyl-(7-tridecyl)silane {4-Br-C 6 H 4 C CSiMe 2 [CH(n-C 6 H 13 ) 2 ]}. To a solution of dichlorodimethylsilane (0.65 ml, 5.0 mmol) in 10 ml of THF at 0 C was added dropwise 2.0 mmol of a Grignard reagent prepared from 7-bromotridecane (660 mg, 2.5 mmol) and magnesium turnings (60 mg, 2.5 mmol) in 7 ml of THF at 70 C. After stirring overnight at room temperature, the mixture was concentrated under vacuum and dissolved in 5 ml of THF again. This solution was then added dropwise to another solution of 4-bromophenyl alkylnyl magnesium bromide in 5 ml of THF, which was prepared in situ from 1-bromo-4-ethylnylbenzene (360 mg, 2.0 mmol) and i-prmgbr (2.9 ml of 0.70 M THF solution, 2.0 mmol). The mixture was stirred at room temperature for 4 days. The reaction was then quenched by 5.0 ml of saturated aqueous ammonium chloride solution. After extraction with ethyl acetate, the combined organic phase was concentrated and subjected to flash column chromatography to afford the desired product (180 mg, 21%) and the unreacted starting material 1-bromo-4-ethylnylbenzene (140 mg, 40%). 1 H NMR (CDCl 3 ): δ 0.21 (s, 6H, SiMe 2 ), 0.75 (m, 1H, SiCH), 0.88 (t, J = 6.90 Hz, 6H, 2CH 2 CH 3 ), (m, 20H, 10CH 2 ), 7.30 (d, J = 8.00 Hz, 2H, ArH), 7.43 (d, J = 8.05 Hz, 2H, ArH). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (2C), (2C, 2CH 2 CH 3 ), (1C), (2C, 2CH 2 ), (4C, 4CH 2 ), (2C, 2CH 2 ), (C CSi), (C CSi), , , (2C), (2C). Br Br H 1. Mg, THF Br Si 2. Me 2 SiCl 2 iprmgbr A General Procedure for the Penta-addition to C 60. A solution of 4-bromophenylethynyl trimethylsilane (R = Me, 607 mg, 2.4 mmol) in 8 ml of THF was added to magnesium turnings (60 mg, 2.5 mmol) in 2 ml of THF. The mixture was stirred at room temperature for 3 hours to give the corresponding Grignard reagent, to which 512 mg (2.5 mmol) of copper bromide dimethyl sulfide complex was added. 10 min later, a solution of C 60 (144 mg, 0.2 mmol) in 10 ml of o-dichlorobenzene was S4
5 added in one portion. After reaction for 2 hours at room temperature, 1.24 ml (20 mmol) of iodomethane was then added. The reaction was quenched by 0.1 ml of a saturated aqueous ammonium chloride solution after stirring for another 3 hours. Toluene (20 ml) was added, and the mixture was filtered through a pad of silica gel. The concentrated residue was purified by flash column chromatography to give 290 mg of 1 in a yield of 90%. The molecules 2 7 were synthesized in the same way from the corresponding phenyl bromide prepared above. Br SiMe 2 R R Si 1. Mg, THF 1. C 60/ODCB 2. CuBrSMe 2 2. MeI R Si Me R Si R Si Si R 1: R = Me, 90% 2: R = n-bu, 89% 3: R = n-c 8 H 17, 92% 4: R = n-c 10 H 21, 86% 5: R = n-c 12 H 25, 93% 6: R = n-c 14 H 29, 90% 7: R = 86% 6,9,12,15,18-Pentakis(4-trimethylsilylethynylphenyl)-1-methyl-1,6,9,12,15,18-hexah ydro(c 60 -I h )[5,6]fullerene (1). 1 H NMR (CDCl 3 ): δ 0.21 (s, 9H, SiMe 3 ), 0.28 (s, 18H, SiMe 3 ), 0.30 (s, 18H, SiMe 3 ), 1.36 (s, 3H, C 60 Me), 7.07 (d, J = 8.00 Hz, 2H, ArH), 7.20 (d, J = 8.00 Hz, 2H, ArH), 7.44 (d, J = 8.00 Hz, 4H, ArH), 7.46 (d, J = 8.00 Hz, 4H, ArH), 7.60 (d, J = 8.00 Hz, 4H, ArH), 7.71 (d, J = 8.00 Hz, 4H, ArH). 13 C NMR (CDCl 3 ): δ (3C, SiMe 3 ), (6C, 2SiMe 3 ), (6C, 2SiMe 3 ), (C 60 Me), (2C, 2C 60 (C α )), (2C, 2C 60 (C α )), (1C, C 60 (C α )), (1C, C 60 (CMe)), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), (1C, Ar), (2C, Ar), (2C, Ar), (4C, Ar), (4C, Ar), (2C, Ar), (2C, Ar), (4C, Ar), (4C, Ar), , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-MS ( ): m/z 1600 [M - ]. APCI-HRMS ( ): calcd for C 116 H 68 Si 5 [M - ] , found ,9,12,15,18-Pentakis(4- n butyldimethylsilylethynylphenyl)-1-methyl-1,6,9,12,15,18- hexahydro(c 60 -I h )[5,6]fullerene (2). 1 H NMR (CDCl 3 ): δ 0.16 (s, 6H, SiMe 2 ), 0.25 (s, 12H, 2SiMe 2 ), 0.28 (s, 12H, 2SiMe 2 ), 0.63 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.73 (m, 8H, S5
6 4SiCH 2 ), 0.93 (m, 15H, 5CH 2 CH 3 ), (m, 20H, 10CH 2 ), 1.45 (s, 3H, C 60 Me, overlapped), 7.08 (d, J = 8.60 Hz, 2H), 7.20 (d, J = 8.00 Hz, 2H), 7.46 (m, 8H), 7.60 (d, J = 8.00 Hz, 4H), 7.72 (d, J = 8.60 Hz, 4H). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (4C, 2SiMe 2 ), (4C, 2SiMe 2 ), (5C, 5SiCH 2 ), (5C, 5CH 2 CH 3 ), (5C, 5CH 2 ), (5C, 5CH 2 ), (C 60 Me), (2C, 2C 60 (sp 3 )), (2C, 2C 60 (sp 3 )), (1C, C 60 (sp 3 )), (1C, C 60 (C)Me), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-HRMS ( ): calcd for C 131 H 98 Si 5 [M - ] , found ,9,12,15,18-Pentakis(4- n octyldimethylsilylethynylphenyl)-1-methyl-1,6,9,12,15,18- hexahydro(c 60 -I h )[5,6]fullerene (3). 1 H NMR (CDCl 3 ): δ 0.17 (s, 6H, SiMe 2 ), 0.25 (s, 12H, 2SiMe 2 ), 0.28 (s, 12H, 2SiMe 2 ), 0.63 (t, J = 8.60 Hz, 2H, SiCH 2 ), 0.74 (m, 8H, 4SiCH 2 ), 0.87 (m, 15H, 5CH 2 CH 3 ), (m, 63H, C 60 Me + 30CH 2, overlapped), 7.09 (d, J = 8.60 Hz, 2H), 7.21 (d, J = 8.05 Hz, 2H), 7.44 (d, J = 8.00 Hz, 4H), 7.46 (d, J = 8.05 Hz, 4H), 7.60 (d, J = 8.05 Hz, 4H), 7.72 (d, J = 8.60 Hz, 4H). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (4C, 2SiMe 2 ), (4C, 2SiMe 2 ), (5C, 5SiCH 2 ), (1C, CH 2 CH 3 ), (2C, 2CH 2 CH 3 ), (2C, 2CH 2 CH 3 ), (1C, CH 2 ), (4C, 4CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (10C, 10CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (C 60 Me), (2C, 2C 60 (sp 3 )), (2C, 2C 60 (sp 3 )), (1C, C 60 (sp 3 )), (1C, C 60 (C)Me), (1C, C CSi), (4C, 4C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-HRMS ( ): calcd for C 151 H 138 Si 5 [M - ] , found ,9,12,15,18-Pentakis(4- n decyldimethylsilylethynylphenyl)-1-methyl-1,6,9,12,15,18- hexahydro(c 60 -I h )[5,6]fullerene (4). 1 H NMR (CDCl 3 ): δ 0.16 (s, 6H, SiMe 2 ), 0.25 (s, 12H, 2SiMe 2 ), 0.27 (s, 12H, 2SiMe 2 ), 0.64 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.72 (m, 8H, S6
7 4SiCH 2 ), 0.87 (m, 15H, 5CH 2 CH 3 ), (m, 83H, C 60 Me + 40CH 2, overlapped), 7.08 (d, J = 8.00 Hz, 2H), 7.20 (d, J = 8.00 Hz, 2H), 7.44 (d, J = 8.05 Hz, 4H), 7.46 (d, J = 8.00 Hz, 4H), 7.60 (d, J = 8.00 Hz, 4H), 7.71 (d, J = 8.00 Hz, 4H). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (4C, 2SiMe 2 ), (4C, 2SiMe 2 ), (5C, 5SiCH 2 ), (1C, CH 2 CH 3 ), (2C, 2CH 2 CH 3 ), (2C, 2CH 2 CH 3 ), (5C, 5CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (m, 10C, 10CH 2 ), (m, 10C, 10CH 2 ), (5C, 5CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (C 60 Me), (2C, 2C 60 (sp 3 )), (2C, 2C 60 (sp 3 )), (1C, C 60 (sp 3 )), (1C, C 60 (C)Me), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-HRMS ( ): calcd for C 161 H 159 Si 5 [M - + H] , found ,9,12,15,18-Pentakis(4- n dodecyldimethylsilylethynylphenyl)-1-methyl-1,6,9,12,15,1 8-hexahydro(C 60 -I h )[5,6]fullerene (5). 1 H NMR (CDCl 3 ): δ 0.17 (s, 6H, SiMe 2 ), 0.25 (s, 12H, 2SiMe 2 ), 0.28 (s, 12H, 2SiMe 2 ), 0.64 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.74 (m, 8H, 4SiCH 2 ), 0.87 (m, 15H, 5CH 2 CH 3 ), (m, 103H, C 60 Me + 50CH 2, overlapped), 7.08 (d, J = 8.55 Hz, 2H), 7.20 (d, J = 8.55 Hz, 2H), 7.44 (d, J = 8.00 Hz, 4H), 7.46 (d, J = 8.00 Hz, 4H), 7.60 (d, J = 8.60 Hz, 4H), 7.71 (d, J = 8.00 Hz, 4H). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (4C, 2SiMe 2 ), (4C, 2SiMe 2 ), (5C, 5SiCH 2 ), (1C, CH 2 CH 3 ), (2C, 2CH 2 CH 3 ), (2C, 2CH 2 CH 3 ), (5C, 5CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (10C, 10CH 2 ), (m, 20C, 20CH 2 ), (5C, 5CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (C 60 Me), (2C, 2C 60 (sp 3 )), (2C, 2C 60 (sp 3 )), (1C, C 60 (sp 3 )), (1C, C 60 (C)Me), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-MS ( ): m/z 2371 [M - ]. APCI-HRMS ( ): calcd for C 171 H 177 Si 5 [M - H] , found S7
8 6,9,12,15,18-Pentakis(4- n tetradecyldimethylsilylethynylphenyl)-1-methyl-1,6,9,12,1 5,18-hexahydro(C 60 -I h )[5,6]fullerene (6). 1 H NMR (CDCl 3 ): δ 0.19 (s, 6H, SiMe 2 ), 0.27 (s, 12H, 2SiMe 2 ), 0.30 (s, 12H, 2SiMe 2 ), 0.66 (t, J = 8.00 Hz, 2H, SiCH 2 ), 0.74 (m, 8H, 4SiCH 2 ), 0.89 (m, 15H, 5CH 2 CH 3 ), (m, 123H, C 60 Me + 60CH 2, overlapped), 7.10 (d, J = 8.05 Hz, 2H), 7.22 (d, J = 8.05 Hz, 2H), 7.45 (d, J = 8.00 Hz, 4H), 7.48 (d, J = 8.00 Hz, 4H), 7.62 (d, J = 8.00 Hz, 4H), 7.73 (d, J = 8.00 Hz, 4H). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (4C, 2SiMe 2 ), (4C, 2SiMe 2 ), (5C, 5SiCH 2 ), (1C, CH 2 CH 3 ), (4C, 4CH 2 CH 3 ), (5C, 5CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (10C, 10CH 2 ), (m, 30C, 30CH 2 ), (5C, 5CH 2 ), (1C, CH 2 ), (4C, 4CH 2 ), (C 60 Me), (2C, 2C 60 (sp 3 )), (2C, 2C 60 (sp 3 )), (1C, C 60 (sp 3 )), (1C, C 60 (C)Me), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-MS (-): m/z 2511 [M - ]. APCI-HRMS ( ): calcd for C 161 H 159 Si 5 [M - ] , found ,9,12,15,18-Pentakis[4-(7-tridecyl)dimethylsilylethynylphenyl]-1-methyl-1,6,9,12,1 5,18-hexahydro(C 60 -I h )[5,6]fullerene (7). 1 H NMR (CDCl 3 ): δ 0.15 (s, 6H, SiMe 2 ), 0.24 (s, 12H, 2SiMe 2 ), 0.26 (s, 12H, 2SiMe 2 ), (m, 35H, 5SiCH, 10CH 2 CH 3, overlapped), (m, 103H, C 60 Me + 50CH 2, overlapped), 7.09 (d, J = 8.00 Hz, 2H), 7.19 (d, J = 8.60 Hz, 2H), 7.42 (d, J = 8.60 Hz, 4H), 7.45 (d, J = 8.60 Hz, 4H), 7.60 (d, J = 8.60 Hz, 4H), 7.71 (d, J = 8.60 Hz, 4H). 13 C NMR (CDCl 3 ): δ (2C, SiMe 2 ), (8C, 4SiMe 2 ), (10C), (10C), (1C), (2C), (2C), (m, 10C), (m, 20C), (10C), (C 60 Me), (2C, 2C 60 (sp 3 )), (2C, 2C 60 (sp 3 )), (1C, C 60 (sp 3 )), (1C, C 60 (C)Me), (1C, C CSi), (4C, 4C CSi), (1C, C CSi), (2C, 2C CSi), (2C, 2C CSi), 122,33, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , APCI-MS ( ): m/z 2441 [M - ]. APCI-HRMS ( ): calcd for C 176 H 188 Si 5 [M - ] , found S8
9 2. Single Crystal X-ray Crystallographic Analysis of 1 and 2 Single crystals of 1 and 2 suitable for X-ray diffraction studies were mounted on a MacScience DIP2030 Imaging Plate diffractometer using MoKα (graphite monochromated, λ = Å) radiation. Crystal data and data statistics are summarized in Table S1. The structures of 1 (toluene) 2 and 2 were solved by the directed method (SHELXS-97). The positional and thermal parameters of non-hydrogen atoms were refined anisotropically on F 2 by the full-matrix least-squares method, using SHELXL-97. Parameters of butyl carbon atoms in 2 were refined isotropically with restraints on the bond lengths and angles, due to fluctuation of the butyl groups. Hydrogen atoms were placed at calculated positions and refined with riding mode on their corresponding carbon atoms. In the subsequent refinement, the function Σω(F o2 F c2 ) 2 was minimized, where F o and F c are the observed and calculated structure factor amplitudes, respectively. The agreement indices are defined as R1 = Σ ( F o - F c )/Σ F o and wr2 = [Σω (F 2 o F 2 c ) 2 /Σ (ωf 4 o )] 1/2. Both crystals contain disorder problems in the five side chains and solvent molecules. This is the reason of high R values and low data completeness. Figure S1. Molecular structure of 1. (a) Side view. (b) Top view. S9
10 Figure S2. Molecular structure of 2. Table S1. Crystal data and data collection parameters for 1 and 2. 1 (toluene) 2 2 crystal system triclinic monoclinic space group P-1 (No. 2) P2 1 /n (No. 14) a, Å (3) (2) b, Å (6) (2) c, Å (7) (2) α, degree (1) 90 β, degree (2) (6) γ, degree (2) 90 V, Å Z 2 4 T, K 153(2) 153(2) crystal size, mm θ min, 2θ max, degree 4.52, , no. of refl. (unique) no. of refl. (I>2σ(I)) no. of parameters R1, wr2 (all data) 0.296, , R, wr (I>2σ(I)) 0.178, , GOF on F Δ, e Å , , 0.66 S10
11 Figure S3. (a) Layered crystal packing of 2. View along the (120) axis. (b) Side view of an interdigitated dimer of 2. Each molecule serves as a part of the neighboring layer. (c) Top view of the interdigitated dimer. Lamellar organization. The large cavity in crystal structure in 1 was filled with solvent. In the liquid crystalline compound 4, it was filled with alkyl groups and they have similar interlayer distance. Figure S4. Schematic drawing of supramolecular organization in 4. S11
12 3. Optical Textures of Liquid Crystals (a) (b) Figure S5. Optical texture of thermotropic liquid crystal C60Me[C6 H4C CSiMe2(n-C10 H21)]5 (4) under optical polarized microscope. (a) Batonnet texture at 150 C on the first heating. (b) Baton-like texture at 130 C on cooling from isotropic liquid over 9 hrs at a rate of 0.1 C/min. S12
13 4. DSC Measurement of Liquid Crystals Figure S6. DSC curves on the second heating of liquid crystals 3, 4, 5, and 6 with alkyl chains number n = 8, 10, 12, and 14, respectively. Table S2. Phase transition behavior of the LC molecules 3-6 on the second heating a C 60 Me(C 6 H 4 C CSiMe 2 C n H 2n+1 ) 5 n Phase transition temperature ( C) [Transition enthalpy (kj/mol)] 3 8 G 140 Sm 223 [1.4] 4 10 G 48 Sm [3.5] 12 G 19 Sm G 11 [3.3] [3.1] Sm 126 [0.8] a Abbreviations: G, glassy; Sm, smectic phase; Iso, isotropic liquid; Cr, crystalline. Transition temperature was determined by DSC at the rate of 10 C min -1 and were taken at the maximum of each transition peak or mid temperature (for glassy/lc transition). Iso Iso Iso Iso S13
14 5. X-ray Diffraction Data for Liquid Crystals Figure S7. X-ray diffraction pattern of thermotropic liquid crystal C 60 Me[C 6 H 4 C CSiMe 2 (n-c 10 H 21 )] 5 (4). (a) At room temperature. (b) After heating at 130 C for 2 hrs. (c) After heating at 130 C for 7 hrs. (d) Standing at 130 C for 10 hrs after cooling from isotropic liquid (190 C). Figure S8. Simulated X-ray diffraction pattern based on single crystal X-ray crystallographic analysis. (a) Pattern for C 60 Me[C 6 H 4 C CSiMe 3 ] 5 (toluene) 2 (1 (toluene) 2 ). (a) Pattern for C 60 Me[C 6 H 4 C CSiMe 2 n Bu] 5 (2). S14
15 Figure S9. X-ray diffraction pattern at 100 C. (a) Compound 5. (b) Compound 6. Table S3. Relationship between the interlayer distance and the atom length (n) of the alkyl chains on the molecules C 60 Me[C 6 H 4 C CSiMe 2 (n-c n H 2n+1 )] 5 with a layered structure. a C 60 Me(C 6 H 4 C CSiMe 2 C n H 2n+1 ) 5 n Interlayer distance (Å) a The interlayer distance of 1 and 2 was determined by X-ray analysis of their single crystals at 120 C. The interlayer distance of 3, 4, 5, and 6 was determined by X-ray diffraction at 180 C, 130 C, 110 C, and 100 C on the first heating process respectively. Figure S10. Relationship between the interlayer distance and the atom length (n) of the alkyl chains on the molecules C 60 Me[C 6 H 4 C CSiMe 2 (n-c n H 2n+1 )] 5 with a layered structure. Note that the crystals of 1 contain toluene molecules in the interlayer space and hence may show a larger interlayer distance. Note that the crystals of 1 contain toluene molecules in the interlayer space and hence may show a larger interlayer distance. S15
Supporting Information. Corporation, 1-1 Kurosakishiroishi, Yahatanishi-ku, Kitakyushu , Japan
Supporting Information Facile Fullerene Modification: FeCl 3 -mediated Quantitative Conversion of C 60 to Polyarylated Fullerenes Containing Pentaaryl(chloro)[60]fullerenes Masahiko Hashiguchi,*,1 Kazuhiro
More information1G (bottom) with the phase-transition temperatures in C and associated enthalpy changes (in
Supplementary Figure 1. Optical properties of 1 in various solvents. UV/Vis (left axis) and fluorescence spectra (right axis, ex = 420 nm) of 1 in hexane (blue lines), toluene (green lines), THF (yellow
More informationPhotostability of a dyad of magnesium porphyrin and fullerene and its application to photocurrent conversion
Supplementary Information Photostability of a dyad of magnesium porphyrin and fullerene and its application to photocurrent conversion Takahiko Ichiki, Yutaka Matsuo,* and Eiichi akamura* Department of
More informationSupplementary Information
Supplementary Information C aryl -C alkyl bond formation from Cu(ClO 4 ) 2 -mediated oxidative cross coupling reaction between arenes and alkyllithium reagents through structurally well-defined Ar-Cu(III)
More informationSupporting Information for. an Equatorial Diadduct: Evidence for an Electrophilic Carbanion
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
More informationPrabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra*
Supporting Information Ferrocenyl BODIPYs: Synthesis, Structure and Properties Prabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra* Department of Chemistry, Indian Institute of Technology
More informationElectronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones
Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones Daisuke Uraguchi, Takaki Ito, Shinji Nakamura, and Takashi oi* Department of Applied Chemistry, Graduate School
More informationA Sumanene-based Aryne, Sumanyne
A Sumanene-based Aryne, Sumanyne Niti Ngamsomprasert, Yumi Yakiyama, and Hidehiro Sakurai* Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871
More informationEnantioselective Conjugate Addition of 3-Fluoro-Oxindoles to. Vinyl Sulfone: An Organocatalytic Access to Chiral. 3-Fluoro-3-Substituted Oxindoles
Enantioselective Conjugate Addition of 3-Fluoro-Oxindoles to Vinyl Sulfone: An Organocatalytic Access to Chiral 3-Fluoro-3-Substituted Oxindoles Xiaowei Dou and Yixin Lu * Department of Chemistry & Medicinal
More informationSupporting Information
Supporting Information Wiley-VCH 2012 69451 Weinheim, Germany Substitution of Two Fluorine Atoms in a Trifluoromethyl Group: Regioselective Synthesis of 3-Fluoropyrazoles** Kohei Fuchibe, Masaki Takahashi,
More informationHighly stereocontrolled synthesis of trans-enediynes via
Supporting Information for Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes Tsutomu Konno*, Misato Kishi, and Takashi Ishihara Address: Department of Chemistry
More informationSupporting Information
Supporting Information Calix[4, 5]tetrolarenes: A New Family of Macrocycles Yossi Zafrani* and Yoram Cohen* School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Ramat Aviv 69978,
More informationSupplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
Supplementary Information for: Scrambling Reaction between Polymers Prepared by Step-growth and Chain-growth Polymerizations: Macromolecular Cross-metathesis between 1,4-Polybutadiene and Olefin-containing
More informationSupporting Information 1. Rhodium-catalyzed asymmetric hydroalkoxylation and hydrosufenylation of diphenylphosphinylallenes
Supporting Information 1 Rhodium-catalyzed asymmetric hydroalkoxylation and hydrosufenylation of diphenylphosphinylallenes Takahiro Kawamoto, Sho Hirabayashi, Xun-Xiang Guo, Takahiro Nishimura,* and Tamio
More informationguanidine bisurea bifunctional organocatalyst
Supporting Information for Asymmetric -amination of -keto esters using a guanidine bisurea bifunctional organocatalyst Minami Odagi* 1, Yoshiharu Yamamoto 1 and Kazuo Nagasawa* 1 Address: 1 Department
More informationSupporting Information
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 Tuning the Lewis Acidity of Boranes in rustrated Lewis Pair Chemistry: Implications for the Hydrogenation of Electron-Poor
More informationSupporting Information
Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2015 A rare case of a dye co-crystal showing better dyeing performance Hui-Fen Qian, Yin-Ge Wang,
More informationSynthesis and Properties of Endohedral Aza[60]fullerenes: and as Their Dimers and Monomers
Supporting Information Synthesis and Properties of Endohedral Aza[60]fullerenes: H2O@C59N and H2@C59N as Their Dimers and Monomers Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, and Yasujiro
More informationEffect of Conjugation and Aromaticity of 3,6 Di-substituted Carbazole On Triplet Energy
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2018 Electronic Supporting Information (ESI) for Effect of Conjugation and Aromaticity of 3,6 Di-substituted
More informationAggregation-induced emission enhancement based on 11,11,12,12,-tetracyano-9,10-anthraquinodimethane
Electronic Supplementary Information (ESI) Aggregation-induced emission enhancement based on 11,11,12,12,-tetracyano-9,10-anthraquinodimethane Jie Liu, ab Qing Meng, a Xiaotao Zhang, a Xiuqiang Lu, a Ping
More informationHighly Luminescent -Conjugated Dithienometalloles: Photophysical Properties and Application to Organic Light-Emitting Diodes
Electronic Supplementary Information (ESI) Highly Luminescent -Conjugated Dithienometalloles: Photophysical Properties and Application to Organic Light-Emitting Diodes Ryosuke Kondo, a Takuma Yasuda,*
More informationSequential dynamic structuralisation by in situ production of
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Electronic Supplementary Information Sequential dynamic structuralisation by in situ production
More informationSelective total encapsulation of the sulfate anion by neutral nano-jars
Supporting Information for Selective total encapsulation of the sulfate anion by neutral nano-jars Isurika R. Fernando, Stuart A. Surmann, Alexander A. Urech, Alexander M. Poulsen and Gellert Mezei* Department
More informationDavid L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information
Experimental Supporting Information for Experimental and DFT Studies Explain Solvent Control of C-H Activation and Product Selectivity in the Rh(III)-Catalyzed Formation of eutral and Cationic Heterocycles
More informationSynthesis of two novel indolo[3,2-b]carbazole derivatives with aggregation-enhanced emission property
Supporting Information for: Synthesis of two novel indolo[3,2-b]carbazole derivatives with aggregation-enhanced emission property Wen-Bin Jia, Hao-Wei Wang, Long-Mei Yang, Hong-Bo Lu, Lin Kong, Yu-Peng
More informationSupporting Information
Supporting Information Enantioselective Synthesis of 3-Alkynyl-3-Hydroxyindolin-2-ones by Copper-Catalyzed Asymmetric Addition of Terminal Alkynes to Isatins Ning Xu, Da-Wei Gu, Jing Zi, Xin-Yan Wu, and
More informationHai-Bin Yang, Xing Fan, Yin Wei,* Min Shi*
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2015 Solvent-controlled Nucleophilic Trifloromethylthiolation of Morita- Baylis-Hillman
More informationHalogen halogen interactions in diiodo-xylenes
Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2016 Electronic Supplementary Information (ESI) for CrystEngComm. This journal is The Royal Society
More informationStereoselective Synthesis of (-) Acanthoic Acid
1 Stereoselective Synthesis of (-) Acanthoic Acid Taotao Ling, Bryan A. Kramer, Michael A. Palladino, and Emmanuel A. Theodorakis* Department of Chemistry and Biochemistry, University of California, San
More informationAccessory Information
Accessory Information Synthesis of 5-phenyl 2-Functionalized Pyrroles by amino Heck and tandem amino Heck Carbonylation reactions Shazia Zaman, *A,B Mitsuru Kitamura B, C and Andrew D. Abell A *A Department
More informationSupporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information Unmasking Representative Structures of TMP-Active Hauser and Turbo Hauser Bases Pablo García-Álvarez, David V. Graham,
More informationHow to build and race a fast nanocar Synthesis Information
How to build and race a fast nanocar Synthesis Information Grant Simpson, Victor Garcia-Lopez, Phillip Petemeier, Leonhard Grill*, and James M. Tour*, Department of Physical Chemistry, University of Graz,
More informationStructural Elucidation of Sumanene and Generation of its Benzylic Anions
Structural Elucidation of Sumanene and Generation of its Benzylic Anions idehiro Sakurai, Taro Daiko, iroyuki Sakane, Toru Amaya, and Toshikazu irao Department of Applied Chemistry, Graduate School of
More informationThe First Asymmetric Total Syntheses and. Determination of Absolute Configurations of. Xestodecalactones B and C
Supporting Information The First Asymmetric Total Syntheses and Determination of Absolute Configurations of Xestodecalactones B and C Qiren Liang, Jiyong Zhang, Weiguo Quan, Yongquan Sun, Xuegong She*,,
More informationSupporting Information. DBU-Mediated Metal-Free Oxidative Cyanation of α-amino. Carbonyl Compounds: Using Molecular Oxygen as the Oxidant
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information DBU-Mediated Metal-Free Oxidative Cyanation of α-amino
More informationSupporting Information for:
Supporting Information for: Photoenolization of 2-(2-Methyl Benzoyl) Benzoic Acid, Methyl Ester: The Effect of The Lifetime of the E Photoenol on the Photochemistry Armands Konosonoks, P. John Wright,
More informationTotal Synthesis of Gonytolides C and G, Lachnone C, and. Formal Synthesis of Blennolide C and Diversonol
. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Total Synthesis of Gonytolides C and G, Lachnone C, and Formal Synthesis
More informationAn Efficient Total Synthesis and Absolute Configuration. Determination of Varitriol
An Efficient Total Synthesis and Absolute Configuration Determination of Varitriol Ryan T. Clemens and Michael P. Jennings * Department of Chemistry, University of Alabama, 500 Campus Dr. Tuscaloosa, AL
More informationChiral Sila[1]ferrocenophanes
Supporting Information Thermal Ring-Opening Polymerization of Planar- Chiral Sila[1]ferrocenophanes Elaheh Khozeimeh Sarbisheh, Jose Esteban Flores, Brady Anderson, Jianfeng Zhu, # and Jens Müller*, Department
More informationSupporting Information
Supporting Information Total Synthesis of (±)-Grandilodine B Chunyu Wang, Zhonglei Wang, Xiaoni Xie, Xiaotong Yao, Guang Li, and Liansuo Zu* School of Pharmaceutical Sciences, Tsinghua University, Beijing,
More informationSupporting Information
Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Supporting Information Rhodium(III)-Catalyzed Formal xidative [4+1] Cycloaddition
More informationSimple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their Labile Dimethylsulfide Adducts
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information for: Simple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their
More informationSupporting Information
Supporting Information (Tetrahedron. Lett.) Cavitands with Inwardly and Outwardly Directed Functional Groups Mao Kanaura a, Kouhei Ito a, Michael P. Schramm b, Dariush Ajami c, and Tetsuo Iwasawa a * a
More informationSyntheses and Structures of Mono-, Di- and Tetranuclear Rhodium or Iridium Complexes of Thiacalix[4]arene Derivatives
Supplementary Information Syntheses and Structures of Mono-, Di- and Tetranuclear Rhodium or Iridium Complexes of Thiacalix[4]arene Derivatives Kenji Hirata, Toshiaki Suzuki, Ai Noya, Izuru Takei and Masanobu
More informationSignificant improvement of dye-sensitized solar cell. performance by a slim phenothiazine based dyes
Significant improvement of dye-sensitized solar cell performance by a slim phenothiazine based dyes Yong Hua, a Shuai Chang, b Dandan Huang, c Xuan Zhou, a Xunjin Zhu, *a,d Jianzhang Zhao, c Tao Chen,
More informationCo(I)-Mediated Removal of Addends on the C60 Cage and Formation of Monovalent Cobalt Complex CpCo(CO)(η 2 -C60)
Supporting Information Co(I)-Mediated Removal of Addends on the C60 Cage and Formation of Monovalent Cobalt Complex CpCo(CO)(η 2 -C60) Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, and Yasujiro
More informationhydroxyanthraquinones related to proisocrinins
Supporting Information for Regiodefined synthesis of brominated hydroxyanthraquinones related to proisocrinins Joyeeta Roy, Tanushree Mal, Supriti Jana and Dipakranjan Mal* Address: Department of Chemistry,
More informationHydrogen Bonded Dimer Stacking Induced Emission of Amino-Benzoic Acid Compounds
Electronic Supplementary Information (ESI) Hydrogen Bonded Dimer Stacking Induced Emission of Amino-Benzoic Acid Compounds Tianlei Zhou, Feng Li, Yan Fan, Weifeng Song, Xiaoyue Mu, Hongyu Zhang* and Yue
More informationDerivatives. Republic. Supporting Information. Index. General Considerations. Experimental Procedures and Spectroscopic Data
Synthesis of Hexahelicene and 1-Methoxyhexahelicene via Cycloisomerization of Biphenylyl-Naphthalene Derivatives Jan Storch *, Jan Sýkora, Jan Čermák, Jindřich Karban, Ivana Císařová and Aleš Růžička Institute
More informationSupporting Information. Molecular Iodine-Catalyzed Aerobic α,β-diamination of Cyclohexanones with 2- Aminopyrimidine and 2-Aminopyridines
Supporting Information Molecular Iodine-Catalyzed Aerobic α,β-diamination of Cyclohexanones with 2- Aminopyrimidine and 2-Aminopyridines Thanh Binh guyen,* Ludmila Ermolenko, Pascal Retailleau, and Ali
More informationSynthesis of Levulinic Acid based Poly(amine-co-ester)s
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2018 Synthesis of Levulinic Acid based Poly(amine-co-ester)s Yann Bernhard, Lucas Pagies, Sylvain
More informationSupplementary Note 1 : Chemical synthesis of (E/Z)-4,8-dimethylnona-2,7-dien-4-ol (4)
Supplementary Note 1 : Chemical synthesis of (E/Z)-4,8-dimethylnona-2,7-dien-4-ol (4) A solution of propenyl magnesium bromide in THF (17.5 mmol) under nitrogen atmosphere was cooled in an ice bath and
More informationDisubstituted Imidazolium-2-Carboxylates as Efficient Precursors to N-Heterocylic Carbene Complexes of Rh, Ir and Pd
J. Am. Chem. Soc. Supporting Information Page S1 Disubstituted Imidazolium-2-Carboxylates as Efficient Precursors to N-Heterocylic Carbene Complexes of Rh, Ir and Pd Adelina Voutchkova, Leah N. Appelhans,
More informationSynthetic Studies on Norissolide; Enantioselective Synthesis of the Norrisane Side Chain
rganic Lett. (Supporting Information) 1 Synthetic Studies on Norissolide; Enantioselective Synthesis of the Norrisane Side Chain Charles Kim, Richard Hoang and Emmanuel A. Theodorakis* Department of Chemistry
More informationElectronic Supplementary Information
Electronic Supplementary Information Regiodivergent Heterocyclization: A Strategy for the Synthesis of Substituted Pyrroles and Furans Using α-formyl Ketene Dithioacetals as Common Precursors Ting Wu,
More informationNanocrystalline Magnesium Oxide-Stabilized Palladium(0): An Efficient and Reusable Catalyst for the Synthesis of N-(2- pyridyl)indoles
Electronic Supplementary Material (ESI) for ew Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre ational de la Recherche Scientifique 2015 Supplementary Material (ESI)
More informationSupporting Information
Supporting Information Synthesis of H-Indazoles from Imidates and Nitrosobenzenes via Synergistic Rhodium/Copper Catalysis Qiang Wang and Xingwei Li* Dalian Institute of Chemical Physics, Chinese Academy
More informationSupporting Information
Cyclo[4]carbazole, An Iodide Anion Macrocyclic Receptor Huangtianzhi Zhu, a Bingbing Shi, a Kexian Chen, b Peifa Wei, a Danyu Xia, a Julfikar Hassan Mondal, a and Feihe Huang* a a State Key Laboratory
More informationSupporting Information
Supporting Information Precision Synthesis of Poly(-hexylpyrrole) and its Diblock Copolymer with Poly(p-phenylene) via Catalyst-Transfer Polycondensation Akihiro Yokoyama, Akira Kato, Ryo Miyakoshi, and
More informationMolecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-on Fluorescent Probe
Supporting Information for Molecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-on Fluorescent Probe Ho Yu Au-Yeung, Jefferson Chan, Teera Chantarojsiri and Christopher J. Chang* Departments
More informationExperimental and Theoretical Investigations of. Surface-Assisted Graphene Nanoribbon Synthesis
Experimental and Theoretical Investigations of Surface-Assisted Graphene Nanoribbon Synthesis Featuring Carbon Fluorine Bond Cleavage Hironobu Hayashi,,, * Junichi Yamaguchi,, Hideyuki Jippo, Ryunosuke
More informationBrønsted Base-Catalyzed Reductive Cyclization of Alkynyl. α-iminoesters through Auto-Tandem Catalysis
Supporting Information Brønsted Base-Catalyzed Reductive Cyclization of Alkynyl α-iminoesters through Auto-Tandem Catalysis Azusa Kondoh, b and Masahiro Terada* a a Department of Chemistry, Graduate School
More informationSupporting Information
Supporting Information Activation of Ene-Diamido Samarium Methoxide with Hydrosilane for Selectively Catalytic Hydrosilylation of Alkenes and Polymerization of Styrene: an Experimental and Theoretical
More informationSupporting Information
Supporting Information New Hexaphosphane Ligands 1,3,5-C 6 H 3 {p-c 6 H 4 N(PX 2 ) 2 } 3 [X = Cl, F, C 6 H 3 OMe(C 3 H 5 )]: Synthesis, Derivatization and, Palladium(II) and Platinum(II) Complexes Sowmya
More informationA Facile and General Approach to 3-((Trifluoromethyl)thio)- 4H-chromen-4-one
A Facile and General Approach to 3-((Trifluoromethyl)thio)- 4H-chromen-4-one Haoyue Xiang and Chunhao Yang* State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy
More informationTetrahydrofuran (THF) was distilled from benzophenone ketyl radical under an argon
SUPPLEMENTARY METHODS Solvents, reagents and synthetic procedures All reactions were carried out under an argon atmosphere unless otherwise specified. Tetrahydrofuran (THF) was distilled from benzophenone
More informationSupporting Information for the Article Entitled
Supporting Information for the Article Entitled Catalytic Production of Isothiocyanates via a Mo(II) / Mo(IV) Cycle for the Soft Sulfur Oxidation of Isonitriles authored by Wesley S. Farrell, Peter Y.
More informationDiastereoselectivity in the Staudinger reaction of. pentafluorosulfanylaldimines and ketimines
Supporting Information for Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines Alexander Penger, Cortney. von ahmann, Alexander S. Filatov and John T. Welch* Address:
More informationSupporting Information
Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany A Highly Enantioselective Brønsted Acid Catalyst for the Strecker Reaction Magnus Rueping, * Erli Sugiono and Cengiz Azap General: Unless otherwise
More informationSupporting Information
Supporting Information N-Heterocyclic Carbene-Catalyzed Chemoselective Cross-Aza-Benzoin Reaction of Enals with Isatin-derived Ketimines: Access to Chiral Quaternary Aminooxindoles Jianfeng Xu 1, Chengli
More informationElectronic Supplementary Information
Electronic Supplementary Information Early-Late Heterobimetallic Rh-Ti and Rh-Zr Complexes via Addition of Early Metal Chlorides to Mono- and Divalent Rhodium Dan A. Smith and Oleg V. Ozerov* Department
More informationActive Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes
Supplementary Information Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes Galyna Dubinina, Hideki Furutachi, and David A. Vicic * Department of Chemistry, University of Hawaii,
More informationA Mild, Catalytic and Highly Selective Method for the Oxidation of α,β- Enones to 1,4-Enediones. Jin-Quan Yu, a and E. J.
A Mild, Catalytic and Highly Selective Method for the Oxidation of α,β- Enones to 1,4-Enediones Jin-Quan Yu, a and E. J. Corey b * a Department of Chemistry, Cambridge University, Cambridge CB2 1EW, United
More informationSupplementary Materials
Supplementary Materials ORTHOGOALLY POSITIOED DIAMIO PYRROLE- AD IMIDAZOLE- COTAIIG POLYAMIDES: SYTHESIS OF 1-(3-SUBSTITUTED-PROPYL)-4- ITROPYRROLE-2-CARBOXYLIC ACID AD 1-(3-CHLOROPROPYL)-4- ITROIMIDAZOLE-2-CARBOXYLIC
More informationElectronic Supplementary Information
Electronic Supplementary Information High-Performance Organic Field-Effect Transisitor based on Dihexyl-Substitued Dibenzo[d,d ]thieno[3,2-b;4,5-b ]dithiophene Yasuo Miyata*, Eiji Yoshikawa, Takeo Minari,
More informationdichloropyrimidine (1.5 g, 10.1 mmol) in THF (10 ml) added at -116 C under nitrogen atmosphere.
Supporting Information Experimental The presence of atropisomerism arising from diastereoisomerism is indicated in the 13 C spectra of the relevant compounds with the second isomer being indicated with
More informationOrganocatalytic asymmetric synthesis of 3,3-disubstituted oxindoles featuring two heteroatoms at C3 position
Organocatalytic asymmetric synthesis of 3,3-disubstituted oxindoles featuring two heteroatoms at C3 position Feng Zhou, Xing-Ping Zeng, Chao Wang, Xiao-Li Zhao, and Jian Zhou* [a] Shanghai Key Laboratory
More informationEnhanced Radical-Scavenging Activity of Naturally-Oriented Artepillin C Derivatives
Supporting nformation Enhanced Radical-Scavenging Activity of Naturally-Oriented Artepillin C Derivatives Sushma Manda, a kuo Nakanishi,* a,b Kei Ohkubo, b Yoshihiro Uto, c Tomonori Kawashima, b Hitoshi
More informationRational design of light-directed dynamic spheres
Electronic Supplementary Information (ESI) Rational design of light-directed dynamic spheres Yumi Okui a and Mina Han* a,b a Department of Chemistry and Department of Electronic Chemistry Tokyo Institute
More informationSensitive and reliable detection of glass transition of polymers. by fluorescent probes based on AIE luminogens
Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting information Sensitive and reliable detection of glass transition of polymers
More informationReversible dioxygen binding on asymmetric dinuclear rhodium centres
Electronic Supporting Information for Reversible dioxygen binding on asymmetric dinuclear rhodium centres Takayuki Nakajima,* Miyuki Sakamoto, Sachi Kurai, Bunsho Kure, Tomoaki Tanase* Department of Chemistry,
More information*Corresponding author. Tel.: , ; fax: ; Materials and Method 2. Preparation of GO nanosheets 3
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Synthesis of 2,3-dihydroquinazolinones and quinazolin-4(3h)-one catalyzed by Graphene Oxide
More informationLewis-Acid Catalysed One Pot Synthesis of Substituted Xanthenes. Supporting Information
Lewis-Acid Catalysed ne Pot Synthesis of Substituted Xanthenes Esther Böß, Tim Hillringhaus, Jacqueline Nitsch and Martin Klussmann Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470
More informationSupporting Information for Synthesis of C(3) Benzofuran Derived Bis-Aryl Quaternary Centers: Approaches to Diazonamide A
Fuerst et al. Synthesis of C(3) Benzofuran Derived Bis-Aryl Quaternary Centers: Approaches to Diazonamide A S1 Supporting Information for Synthesis of C(3) Benzofuran Derived Bis-Aryl Quaternary Centers:
More informationSYNTHESIS OF A 3-THIOMANNOSIDE
Supporting Information SYNTHESIS OF A 3-THIOMANNOSIDE María B Comba, Alejandra G Suárez, Ariel M Sarotti, María I Mangione* and Rolando A Spanevello and Enrique D V Giordano Instituto de Química Rosario,
More informationSupporting Information
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 208 Supporting Information Cobalt-Catalyzed Regioselective Syntheses of Indeno[2,-c]pyridines
More informationSupporting Information
Supporting Information SmI 2 -Mediated Carbon-Carbon Bond Fragmentation in α-aminomethyl Malonates Qiongfeng Xu,, Bin Cheng, $, Xinshan Ye,*, and Hongbin Zhai*,,,$ The State Key Laboratory of Natural and
More informationSynthesis of fluorophosphonylated acyclic nucleotide analogues via Copper (I)- catalyzed Huisgen 1-3 dipolar cycloaddition
Synthesis of fluorophosphonylated acyclic nucleotide analogues via Copper (I)- catalyzed Huisgen 1-3 dipolar cycloaddition Sonia Amel Diab, Antje Hienzch, Cyril Lebargy, Stéphante Guillarme, Emmanuel fund
More informationSupporting Information:
Enantioselective Synthesis of (-)-Codeine and (-)-Morphine Barry M. Trost* and Weiping Tang Department of Chemistry, Stanford University, Stanford, CA 94305-5080 1. Aldehyde 7. Supporting Information:
More informationSupporting Material. 2-Oxo-tetrahydro-1,8-naphthyridine-Based Protein Farnesyltransferase Inhibitors as Antimalarials
Supporting Material 2-Oxo-tetrahydro-1,8-naphthyridine-Based Protein Farnesyltransferase Inhibitors as Antimalarials Srinivas Olepu a, Praveen Kumar Suryadevara a, Kasey Rivas b, Christophe L. M. J. Verlinde
More informationSupporting Information
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Supporting Information Sulfonato-imino copper(ii) complexes : fast and general Chan-
More informationSupporting Information
Supporting Information Manuscript Title: Synthesis of Semibullvalene Derivatives via Co 2 (CO) 8 -Mediated Cyclodimerization of 1,4-Dilithio-1,3-butadienes Corresponding Author: Zhenfeng Xi Affiliations:
More informationSupporting Information. Organocatalytic Synthesis of N-Phenylisoxazolidin-5-ones and a One-Pot Synthesis of -Amino Acid Esters
Supporting Information rganocatalytic Synthesis of N-Phenylisoxazolidin-5-ones and a ne-pot Synthesis of -Amino Acid Esters Jayasree Seayad, Pranab K. Patra, Yugen Zhang,* and Jackie Y. Ying* Institute
More informationSupporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supporting Information TEMPO-catalyzed Synthesis of 5-Substituted Isoxazoles from Propargylic
More informationSupporting Information Configurational Assignments
Supporting Information Configurational Assignments Symmetric Diaryl Sulfoxides as Asymmetric Sulfinylating Reagents for Dialkylmagnesium Compounds Simon Ruppenthal and Reinhard Brückner* Institut für Organische
More informationSupporting Information
Supporting Information Ligand- to- Ligand Interactions Direct Formation of D 2 - Symmetrical Alternating Circular Helicate Tan Yan Bing, Tsuyoshi Kawai* and Junpei Yuasa* Table of Contents Experimental
More informationSupplementary Information. Mapping the Transmission Function of Single-Molecule Junctions
upplementary Information Mapping the Transmission Function of ingle-molecule Junctions Brian Capozzi 1, Jonathan Z. Low 2, Jianlong Xia 3, Zhen-Fei Liu 4, Jeffrey B. Neaton 5,6, Luis M. Campos 2, Latha
More informationPreparation of Optically Pure Tertiary Phosphine Oxides via Addition of P-Stereogenic Secondary Phosphine Oxide to Activated Alkenes
Preparation of Optically Pure Tertiary Phosphine Oxides via Addition of P-Stereogenic Secondary Phosphine Oxide to Activated Alkenes Ji-Ping Wang, Shao-Zhen Nie, Zhong-Yang Zhou, Jing-Jing Ye, Jing-Hong
More informationSupporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003
Supporting Information for Angew. Chem. Int. Ed. Z50567 Wiley-VCH 2003 69451 Weinheim, Germany Metallacarborane-Based Nanostructures: A Carbon-Wired Planar Octagon** Haijun Yao, Michal Sabat, and Russell
More informationOrganocatalytic asymmetric biomimetic transamination of aromatic ketone to optically active amine
Organocatalytic asymmetric biomimetic transamination of aromatic ketone to optically active amine Ying Xie, a Hongjie Pan, a Xiao Xiao, a Songlei Li a and Yian Shi* a,b a Beijing National Laboratory for
More information