Supplementary Methods

Transcription

1 A A Supplementary Methods 1. Materials All the reagents and solvents were of commercial reagent grade and were used without further purification unless otherwise noted. Dichloromethane and 1,2- dichloroethane for reaction medium were distilled over Ca 2 and toluene was distilled over sodium metal. Single-walled carbon nanotubes (SWTs) produced by CVD process using a silica-supported Co-Mo catalyst (CoMoCAT) were purchased from SouthWest anotechnologies, nc Equipments UV VS-R spectral measurements were conducted using UV-3100PC scanning spectrophotometer (Shimadzu Co.). Circular Dichroism spectra were recorded on J-820 and J-600 spectropolarimeters (JASC nternational Co. Ltd.). Photo luminescence spectra were measured on SPEX anolg (oriba Ltd.). Centrifugation was carried out with eckman J2-21M/E. Tip-sonication was performed with MSX (550W, 20 kz). 3. Synthesis of 1,3-bis(10',20'-di(1''-tert-butoxycarbonylamino-2''-phenylethyl)- porphinatozinc()-5'-yl)benzene (chiral nano-tweezers (R)- and (S)-1) Since (R)- and (S)-1 were prepared by the same procedure starting from the corresponding (R)- and (S)-phenylalaninal (Figure S1), the typical procedure for the preparation of (R)-1 is shown below. Finally, the same spectral data on UV-VS, 1 MR and MALD-TF-MS were obtained in (R)- and (S) ,15-Di(1'-tert-butoxycarbonylamino-2'-phenylethyl)porphyrin PhC 2 C 2 t-u t-u 2 C + PhC 2 C 1. TFA, C 2 Cl 2 2. DDQ t-u 2 C C 2 Ph ature Publishing Group

2 A A To a solution of 2,2'-dipyrrylmethane (292 mg, 2.0 mmol) and (R)- phenylalaninal (500 mg, 2.0 mmol) in C 2 Cl 2 (300 ml), trifluoroacetic acid (0.1 ml) was added and the mixture was stirred under Ar for 48 h at room temperature under dark. After the addition of DDQ (740 mg, 3.3 mmol), the mixture was stirred for additional 2 h. The reaction was quenched by the addition of triethylamine, and the reaction mixture was poured into water. The product was extracted with C 2 Cl 2 and purified by column chromatography using alumina and silica gel as stationary phases and C 2 Cl 2 as eluent. Further purification by recrystallization from CCl 3 and acetonitrile gave 5,15-di(1'-tert-butoxycarbonylamino-2'-phenylethyl)porphyrin as purple solid in 19% yield (142 mg). MALD-TF Mass (m/z): (found), (calcd.); UV-VS (CCl 3 ), λ max : 406, 504, 537, 576 and 630 nm; 1 MR (CDCl 3 270Mz), (s, 2, meso-), 9.57(4, β-), 9.38(4, β-), 7.37 (2, phenyl), (m, 8, phenyl), 6.25(2, CC 2 Ph) 4.33(4, CC 2 Ph), 1.39 (s, 18, tertbutyl), 0.85 (s, 2, ), -2.88(s, 2, of pyrrole) romo-10,20-di(1'-tert-butoxycarbonylamino-2'-phenylethyl)- porphinatozinc() PhC 2 C 2 t-u PhC 2 C 2 t-u PhC 2 C 2 t-u S (Ac) 2 r r t-u 2 C C 2 Ph t-u 2 C C 2 Ph t-u 2 C C 2 Ph -romosuccinimide (26.7 mg, 0.15 mmol) was added to a 100 ml CCl 3 solution containing pyridine (1 ml) and 5,15-bis(1'-tert-butoxycarbonylamino-2'- phenylethyl)porphyrin (112 mg, 0.15 mmol) at 0 C. The mixture was stirred for 30 min and the reaction was quenched by the addition of 10 ml of acetone. After stirring for 5 min, the mixture was diluted with water and extracted with CCl 3. The combined extract was washed with water three times, dried over anhydrous a 2 S 4 and passed through a short silica gel column. After concentration, the residue was dissolved into 50 ml CCl 3, (Ac) 2 in methanol was added, and the mixture was refluxed for 2 h. Then, it was cooled down to room temperature, washed with water 3 times and dried over ature Publishing Group

3 A A anhydrous a 2 S 4. After filtration, the filtrate was passed through a short silica gel column to give crude product (120 mg), which was used in the next reaction without further purification (4',4',5',5'-Tetramethyl-[1',3',2']dioxaborolan-2'-yl)-10,20-di(1''-tertbutoxycarbonylamino-2''-phenylethyl)porphinatozinc() 2 PhC 2 C 2 t-u PhC 2 C 2 t-u r + PdCl 2 (PPh 3 ) 2 Kt-u t-u 2 C C 2 Ph t-u 2 C C 2 Ph n a 50 ml round-bottom flask were placed the crude bromide (112 mg), 4,4,5,5,4',4',5',5'-octamethyl-[2,2']bi[[1,3,2]dioxaborolane (76.2 mg, 0.30 mmol), transdichlorobis(triphenylphosphine)palladium() (3.0 mg, mmol), Kt-u (56.0 mg, 0.50 mmol) and 30 ml of 1,2-dichloroethane under Ar. The mixture was stirred at 85 C for 3 h under Ar atmosphere. Then, the reaction was quenched by the addition of 10 ml of KCl aq., washed with water and dried over MgS 4. After concentration, the residue was purified by silica gel column chromatography using C 2 Cl 2 as eluent to give the porphyrylboronate (54.2 mg, yield (39%) is based on the weight (112 mg) of the crude bromide.). UV-Vis(CCl 3 ), λ max : 418, 550, and 583 nm; 1 MR (Me-D 4, 270Mz), (s, 1, meso-), (4, β-), 9.80 (2, β-), 9.41 (2, β-), 8.17 (2, CC 2 Ph), 7.62 (2, phenyl), 7.18 (4, phenyl), 6.96 (4, phenyl), 4.31(4, CC 2 Ph), 1.89 (s, 12, methyl), 1.30 (s, 18, tert-butyl), 0.85 (s, 2, ) ,3-is(10',20'-di(1''-tert-butoxycarbonylamino-2''- phenylethyl)- porphinatozinc()-5'-yl)benzene 3, ature Publishing Group

4 A A PhC2 C2t-u Pd(PPh3)4 + Cs2C3 C2Ph C2Ph t-u2c t-u2c t-u2c C2t-u PhC2 C2Ph PhC2 C2t-u (R)-1 1,3-Diiodobenzene (6.6 mg, mmol), the porphyrylboronate (37.6 mg, mmol), Cs2C3 (39 mg, 0.12 mmol) and Pd(PPh3)4 (2.3 mg, mmol) were dissolved in dry DMF (2.0 ml) and dry toluene (2.0 ml). After deoxygenation, the mixture was heated to 80 C and stirred for 3 h under Ar. Then, the reaction was quenched by the addition of water, and the product was extracted with ether. The combined extract was dried over anhydrous a2s4, passed through a short silica gel column and concentrated. The residue was subjected to recycling preparative GPCPLC to give chiral nano-tweezers 1 as purple solid (14.3 mg, 42% yield). UV-VS (CCl3): λmax : 415, 430, 552 and 589 nm. ES-MS (m/z): (found), (calcd.) ES-Mass of 1 Since decent spectrum of 1 MR of the zinc() diporphyrin was not obtained, the spectral data of free base diporphyrin prepared by the acid-treatment of the zinc() diporphyrin were shown here. 1 MR (CDCl3, 270Mz), (s, 2, meso-), 9.70 (4, β-), 9.51 (4, β-), ature Publishing Group

5 A A 9.39 (4, β-), 9.30 (4, β-) 9.07 (1, m-phenylene), 8.56 (2, m-phenylene), 8.12 (1, m-phenylene), 7.40 (4, phenyl), 7.04 (8, phenyl), 6.91 (8, phenyl), 6.21 (4, CC 2 Ph), 4.34 (8, CC 2 Ph), 1.24 (s, 36, tert-butyl), 0.85 (4, ), -2.83(s, 4, of pyrrole). 1. achilo, S. M. et al. arrow (n,m)-distribution of single-walled carbon nanotubes grown using a solid supported catalyst. J. Am. Chem. Soc. 125, (2003). 2. shiyama, T., Murata, M. & Miyaura,. Palladium(0)-Catalyzed Cross- Coupling Reaction of Alkoxydiboron with aloarenes: A Direct Procedure for Arylboronic Esters. J. rg. Chem. 60, (1995). 3. yslop, A. G., Kellett, M. A., ovine, P. M. & Therien, M. J. Suzuki Porphyrins: ew Synthons for the Fabrication of Porphyrin-Containing Supramolecular Assemblies. J. Am. Chem. Soc. 120, (1998). 4. Peng, X. et al. Dodecameric Porphyrin Wheel. J. Am. Chem. Soc. 126, (2004) ature Publishing Group

6 A A Supplementary Figures t-u 2 C PhC 2 R C C C 2 t-u C 2 Ph S PhC 2 C 2 t-u t-u 2 C C 2 Ph t-u 2 C C 2 Ph (R)-monoporphyrin (S)-monoporphyrin PhC 2 C 2 t-u PhC 2 C 2 t-u t-u 2 C C 2 Ph t-u 2 C C 2 Ph PhC 2 C 2 t-u Pd(PPh 3 ) 4 Cs 2 C 3 DMF/toluene Pd(PPh 3 ) 4 Cs 2 C 3 DMF/toluene 42% yieild 45% yieild PhC 2 t-u 2 C C 2 t-u C 2 Ph PhC 2 t-u 2 C C 2 t-u C 2 Ph PhC 2 C 2 t-u t-u 2 C C 2 Ph Ph 2 C t-u 2 C C 2 Ph C 2 t-u (R)-1 mirror image (S)-1 Figure S1 Synthesis of chiral nano-tweezers via double Suzuki-Miyaura coupling reaction. oth (R)- and (S)-1 were prepared in good yields by the same procedure starting with 2,2 -dipyrrylmethane and the corresponding (R)- and (S)-phenylalaninal derivatives. Ph, t-u and DMF stand for phenyl group, tert-butyl group and,-dimethylformamide, respectively ature Publishing Group

7 A A (6,5) (8,3) (8,4) (7,6) (7,5) Figure S2 Photoluminescence spectra of semiconducting SWTs after extraction with (R)-1. Five kinds of the chiral indices, (6,5), (8,4), (7,5), (8,3) and (7,6) were observed as major components. SWTs extracted with (S)-1 showed a similar photoluminescence spectrum ature Publishing Group

8 A A L:(S)-1 R:(R)-1 L:(R)-1 R:(S) kcal/mol kcal/mol kcal/mol kcal/mol mirror image mirror image L SWTs were enriched by the extraction with (R)-1. Figure S3 Molecular mechanics modeling of the complex structures of R and L SWTs with (R)- and (S)-1. Enthalpy of association is shown below each complex structure. The complexes with mirror-image structures give quite similar energy. (R)- and (S)-1 form more stable complex with L and R SWTs than R and L ones, respectively ature Publishing Group

9 A A Figure S4 UV-VS-R spectra of the washings of the SWTs:(R)-1 complex. The absorbance of Soret band was disappeared after washing with TF twice and pyridine five times, indicating thorough removal of chiral diporphyrin ature Publishing Group

10 A A Figure S5 Transmission electron microscope images of SWTs (CoMoCAT) before (right image) and after (left image) extraction with (R)-1. Most of the metal particles (black dots in the right image) were removed through the extraction ature Publishing Group