Synthesis and Star/Linear Topology Transformation of Mechanically Linked ABC Terpolymer Hiroki Sato,† Daisuke Aoki,† and Toshikazu Takata*,†,‡ †Department of Chemical Science and Engineering and ‡JST-CREST, Tokyo Institute of Technology, O-okayama 2-12-1(H-126), Meguro-ku, Tokyo 152-8552, Japan. [email protected] Supporting Information Table of Contents Materials and Instruments S2 Syntheses of axle (1) and wheel (2) components S3 Syntheses of polymers S6 Characterization of polymers S10 References S10 S1 Materials Dichloromethane was purchased from ASAHI GLASS CO., LTD., and distilled over CaH2 after being washed with water. δ-Valerolactone (δ-VL)(>98%, Tokyo Kasei Kogyo Co., Ltd. (TCI)) was distilled over CaH2 under reduced pressure. Styrene was used after passing through alumina column. Copper(I) bromide (>99%, Wako Pure Chemical Industries, Ltd. (Wako)) was used after washing with conc. hydrobromic acid. 4-hydroxy-3,5-dimethylbenzaldehyde (S1) (>98%, TCI), propargyl bromide (>97%, TCI), lithium aluminium hydride (>80%, Wako), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI·HCl) (>98%, TCI), 4-(dimethylamino)pyridine (DMAP) (>99%, TCI), diphenyl phosphate (DPP) (>99%, TCI), 3,5-bis(trifluoromethyl)phenyl isocyanate (>98%, TCI), toluene (>99%, Wako), 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (TTC-CO2H) (>97%, Sigma-Aldrich Co.), 2,2'-azodiisobutyronitrile (AIBN) (>98%, TCI), N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) (99%, TCI), acetic anhydride (>93%, Wako), triethylamine (>99%, Wako) and tetrahydrofuran (THF) (>99%, anhydrous, Wako) were used as received. 12-aminododecanoate hydrochloride1, wheel-OH2 and azide-terminated PEO3 were prepared according to literatures. Other commercially available regents and solvents were used as received. Instruments 1H (300 MHz) and 13C (75 MHz) NMR spectra were recorded on a Bruker Biospin AVANCE DPX-300 spectrometer and 1H (400 MHz) NMR spectrum was recorded on a JEOL AL-400 spectrometer, using CDCl3 as the solvent, calibrated using tetramethylsilane (δH = 0.00 ppm), CDCl3 (δC = 77.0 ppm) and DMSO-d6 (δC = 39.5 ppm) as internal standards. Gel permeation chromatography (GPC) was performed at 30 °C in CHCl3 (0.85 mL / min) using a JASCO PU-2080 system equipped with a set of Shodex K-804 and Shodex K-805 columns. The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index (Mw/Mn) of the polymers were calculated on the basis of a polystyrene calibration. Preparative GPC was carried out using a HPLC LC-918 instrument by Japan Analytical Industry with a Megapak-Gel 201C. MALDI-TOF mass spectra were taken on a Shimadzu AXIMA-CFR mass spectrometer. The spectrometer was equipped with a nitrogen laser (l = 337 nm) and with pulsed ion extraction. The operation was performed at an accelerating potential of 20 kV by a linear-positive ion mode. The sample polymer solution (1 mg/mL) was prepared in CHCl3, and the matrix, dithranol, and cationizing agent, sodium trifluoroacetate, were dissolved in CHCl3 or CH3CN (20 and 1 mg/mL, respectively), and 50 µL of each solution were mixed prior to MALDI analysis. Thermogravimetric analyses (TGA) were performed with a Shimadzu DTG–60 instruments under nitrogen (heating rate of 10 °C min–1). S2 Synthesis of axle component 1 Br O - + O CHO ClH N C10H20 OMe K CO 3 CHO 2 3 N C H OMe O 10 20 O HO DMF toluene 80 °C, 12 h reflux, 12 h S1 S2 S3 1) HCl, MeOH LiAlH4 2) NH PF , MeOH N C10H20 OH 4 6 N C10H20 OH H H2 THF O O - reflux, 8 h PF6 S4 1 34% 60% To a solution of S1 (10.0 g, 67 mmol) and propargyl bromide (7.0 mL, 81 mmol) in DMF (100 mL) was added potassium carbonate (27.6 g, 0.20 mol) and heated at 80 °C. After 12 h, solvent was removed under reduced pressure and the residue was diluted with chloroform followed by washing with sat. NaHCO3 and brine. The organic layer was dried over MgSO4 followed by evaporation to afford S2 as a brown solid, which was used without further purification. A mixture of S2 (8.00 g, 43 mmol), methyl 12-aminododecanoate hydrochloride (12.0 g, 45 mmol) and toluene (300 mL) was refluxed with a Dean-Stark trap. After 12 h, solvent was removed under reduced pressure to afford S3 as a brown solid, which was used without further purification. To a solution of S3 (26.8 g, 67 mmol) in anhydrous THF (300 mL) was added dropwise a suspension of lithium aluminum hydride (10.0 g, 0.26 mol) in anhydrous THF (1.5 L) at 0 °C, followed by heating temperature to reflux. After 8 h, the reaction was quenched by sat. Na2SO4 at 0 °C. The precipitates were filtered off and the filtrate was evaporated to afford the crude product. Silica column chromatography (eluent: ethyl acetate) yielded S4 (8.40 g, 34%) as a brown solid. 1 H-NMR (400 MHz, 298 K, CDCl3): 6.98 (2H, s), 4.50 (2H, d, 2.4 Hz), 3.68 (2H, s), 3.65 (2H, t, 6.8 Hz), 2.63 (2H, t, 6.8 Hz), 2.52 (1H, t, 2.4 Hz), 2.32 (6H, s), 1.85–1.20 (20H, m). To a solution of S4 (8.40 g, 24 mmol) in the least amount of methanol for solvation was added conc. HCl aq. (10.0 mL, 0.12 mol) at ambient temperature. The mixture was stirred for a few minutes and was poured into a large amount of diethyl ether. The precipitates were collected by filtration and dried in vacuo. To a solution of the obtained precipitates in the least amount of methanol for solvation was added sat. PF6NH4 aq. until the precipitates were formed. The precipitates were collected by filtration, followed by washing with water and drying in vacuo to afford 1 (7.59 g, 60 %) as a brown solid. 1 + H-NMR (400 MHz, 298 K, CDCl3): 7.07 (2H, s, e), 6.57 (brs, —NH2 —), 4.52 (2H, d, 2.4 Hz, g), 4.14 (2H, s, d), 3.62 (2H, t, 6.6 Hz, a), 2.95 (2H, brt, 7.7 Hz, c), 2.51 (1H, t, 2.4 Hz, h), 2.33 (6H, s, f), 1.75– 1.20 (20H, m, b). S3 13 C-NMR (75 MHz, 298 K, DMSO-d6): 155.27, 131.18, 130.33, 127.68, 79.70, 78.02, 60.72, 59.56, 49.68, 46.70, 29.10, 29.00, 28.97, 28.93, 28.80, 28.48, 25.89, 25.52, 25.35, 16.32. + + HR-MS (FAB ): Calcd for C23H42NO3 [M] : 374.3059. Found: 374.3062. 1 Figure S1. Assigned H-NMR spectrum of 1 (400 MHz, 298 K, CDCl3). 13 Figure S2. C-NMR spectrum of 1 (75 MHz, 298 K, DMSO-d6). S4 Synthesis of wheel component 2 O S SC H OH O 12 25 NC S O O EDCI·HCl O O O O O DMAP O O S SC H + HO 12 25 O O S O O O O NC CH2Cl2 O O rt, dark, 4 d wheel-OH TTC-CO2H 2 A solution of wheel-OH (861 mg, 1.8 mmol), TTC-CO2H (811 mg, 2.0 mmol), EDCI·HCl (386 mg, 2.0 mmol) and DMAP (22 mg, 0.18 mmol) in dichloromethane (20 mL) was stirred at ambient temperature under dark. After four days, 20 mL of 0.15 M HCl was added and the aqueous layer was extracted with chloroform three times. The combined organic layer was washed with 0.15 M HCl, sat. NaHCO3 and brine, and dried over MgSO4, followed by evaporation to afford the crude product as yellow oil. Purification by preparative GPC yielded 2 (1.29 g, 83%) as viscous yellow oil. 1 H NMR (300 MHz, 298 K, CDCl3): 6.94–6.80 (7H, m, aromatics), 5.03 (2H, s, a), 4.15 (8H, m, α), 3.93 (8H, m, β), 3.84 (8H, s, γ), 3.32 (2H, t, 7.6 Hz, b), 2.65 (2H, t, 7.6 Hz, c), 1.86 (3H, s, d), 1.7–1.2 (22H, m, alkyl chain), 0.88 (3H, t, 6.7 Hz, e (terminal Me)). 13 C NMR (75 MHz, 298 K, CDCl3): 217.3, 171.7, 149.5, 149.3, 128.9, 122.3, 121.9, 119.4, 115.0, 114.6, 114.1, 71.6, 70.3, 70.2, 9.9, 69.9, 69.8, 67.3, 46.7, 37.5, 34.2, 32.3, 30.2, 30.0, 29.9, 29.8, 29.7, 29.6, 29.3, 28.1, 25.1, 23.1, 14.5. + + HR-MS (ESI ): Calcd for C44H65NNaO10S3 [M+Na] : 886.3663. Found: 886.3652 1 Figure S3. Assigned H-NMR spectrum of 2 (300 MHz, 298 K, CDCl3). S5 13 Figure S4. C-NMR spectrum of 2 (75 MHz, 298 K, CDCl3). Synthesis of macromolecular [2]rotaxane PVLx O S SC H O 12 25 O O NC S S SC H O O 12 25 CF3 O O NC S O O N C10H20 OH (PhO)2P(=O)OH O O CF3 OCN CF3 H2 + O O O O O O O - PF O O N C10H20 O O N CF3 6 CH2Cl2, rt, o/n O H O x H CH2Cl2, rt, 1.5 h O 2 O O - PF6 1 2 PVL33 73% PVL64 48% A mixture of the axle component 1 (50 mg, 0.096 mmol) and a wheel component 2 (90 mg, 0.10 mmol) in dry CH2Cl2 (1.6 mL) was sonicated at ambient temperature until the solution got transparent to afford a solution of the pseudo[2]rotaxane initiator.