SUPPORTING INFORMATION

Transcription

1 Energetically Demanding Transport in a Supramolecular Assembly Chuyang Cheng, Paul R. McGonigal, Wei-Guang Liu, Hao Li, Nicolaas A. Vermeulen, Chenfeng Ke, Marco Frasconi, Charlotte L. Stern, William A. Goddard III, J. Fraser Stoddart * Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States * stoddart@northwestern.edu SUPPORTING INFORMATION Table of Contents 1. General Methods S2 2. Synthetic Procedures S2 3. UV/Vis/NIR Spectroscopy S19 4. Single Crystal X-Ray Diffraction S H NMR Spectroscopy Investigation of Pumping and Dethreading S21 6. DFT Calculations S31 7. Calculation of Energy Conversion Efficiency S49 8. References S51

2 1. General Methods All reagents were purchased from commercial suppliers (Sigma-Aldrich or Fisher) and employed without further purification. Cyclobis(paraquat-p-phenylene) tetrakis(hexafluorophosphate) 1 (CBPQT 4PF 6 ), S6 2 and S8 2PF 3 6 were prepared according to literature procedures. Thin layer chromatography (TLC) was performed on silica gel 60 F254 (E. Merck). Column chromatography was carried out on silica gel 60F (Merck 9385, mm). Solvents used in experiments involving radicals were degassed using the freeze-pump-thaw method. UV/Vis/NIR Spectra were recorded on a Varian 100-Bio UV-Vis spectrophotometer in MeCN at room temperature. Nuclear magnetic resonance (NMR) spectra were recorded on Bruker Avance 600 or Varian P-Inova 500 spectrometers, with working frequencies of 600 and 500 MHz for 1 H, and 150 and 125 MHz for 13 C nuclei, respectively. Chemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvents (CDCl 3 : δ = 7.26 ppm, CD 3 CN: δ =1.94 ppm). High resolution mass spectra were measured on a Finnigan LCQ iontrap mass spectrometer (HR-ESI). 2. Synthetic Procedures S1 PF 6 : A mixture of 3,5-lutidine (1.07 g, 10 mmol) and 1,3-dibromopropane (20 ml) was stirred at 120 C overnight. After cooling to room temperature, the mixture was poured into Et 2 O (50 ml). The resulting suspension was extracted with H 2 O (3 20 ml), then NH 4 PF 6 (2 g) was added to the combined aqueous phase. The precipitate was filtered and washed with H 2 O (3 x 5 ml) to afford S1 PF 6 (3.28 g, 88%). 1 H NMR (500 MHz, CD 3 CN): δ 8.36 (s, 2H), 8.15 (s, 1H), S2

3 4.54 (t, J = 7.2 Hz, 2H), 3.47 (t, J = 6.4 Hz, 2H), (m 8H). 13 C NMR (126 MHz, CD 3 CN): δ 147.5, 142.1, 139.8, 60.3, 33.6, 29.4, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S2 2PF 6 : A mixture of S1 PF 6 (1.87 g, 5 mmol) and 4,4 -bipyridine (0.78 g, 5 mmol) were stirred in MeCN (15 ml) for 2 days. After cooling to room temperature, the mixture was poured into Et 2 O (50 ml). The resulting suspension was filtered and washed with Et 2 O (3 5 ml). The solid was dissolved in H 2 O (50 ml), then NH 4 PF 6 (2 g) was added. The precipitate was filtered and washed with H 2 O (3 5 ml) to afford a crude product, which was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford S2 2PF 6 (1.35 g, 45%) as a white solid. 1 H NMR (500 MHz, CD 3 CN): δ 8.86 (d, J = 6.2 Hz, 2H), 8.77 (d, J = 6.7 Hz, 2H), (m, 4H), 8.19 (s, 1H), 7.80 (d, J = 6.3 Hz, 2H), 4.64 (t, J = 7.6 Hz, 2H), 4.54 (t, J = 7.6 Hz, 2H), 2.64 (p, J = 7.2 Hz, 2H), 2.49 (s, 6H). 13 C NMR (126 MHz, CD 3 CN): δ 155.3, 151.8, 147.8, 145.6, 142.0, 141.6, 140.0, 126.9, 122.4, 58.3 (2 C), 32.2, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = DB0 4PF 6 : A mixture of S1 PF 6 (185 mg, 0.5 mmol) and 4,4 -bipyridine (30 mg, 0.19 mmol) were stirred in MeCN (1 ml) for 7 days. After cooling to room temperature, the mixture was poured into Et 2 O (50 ml). The resulting suspension was filtered and washed with Et 2 O (3 5 S3

4 ml). The solid was dissolved in H 2 O (50 ml), and then NH 4 PF 6 (2 g) was added. The precipitate was filtered and washed with H 2 O (3 5 ml) to afford a crude product, which was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford S3 4PF 6 (1.35 g, 45%) as a colorless solid. 1 H NMR (500 MHz, CD 3 CN): δ 8.91 (d, J = 6.9 Hz, 4H), 8.44 (d, J = 6.9 Hz, 4H), 8.38 (s, 4H), 8.20 (s, 2H), 4.70 (t, J = 8.0 Hz, 4H), 4.55 (d, J = 7.9 Hz, 4H), (m, 4H), 2.50 (s, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 150.0, 146.9, 145.5, 141.1, 139.1, 127.2, 58.0, 57.3, 31.3, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S4

5 S3: A mixture of 2,6-diisopropylphenol (1.78 g, 10 mmol), 6-chlorohexan-1-ol (1.36 g, 10 mmol) and K 2 CO 3 (3.0 g, 22 mmol) was stirred at 100 C in DMF (30 ml) overnight. After cooling to room temperature, the mixture was poured into H 2 O (100 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (100 ml). After drying (MgSO 4 ), the solvent was removed in vacuo to afford a crude precursor (2.6 g) as a light-yellow oil. The crude precursor alcohol, p-toluenesulfonyl chloride (2.0 g, 10.5 mmol) and 4-dimethylaminopyridine (122 mg, 1 mmol) were stirred in Et 3 N (5 ml) and CH 2 Cl 2 (50 ml) at room temperature for 3 h. The solution was poured into H 2 O (50 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (50 ml). After drying (MgSO 4 ), the solvent was removed in vacuo and the resulting residue was purified by column chromatography (SiO 2 : Hexanes / EtOAc 5:1) to afford S3 (3.0 g, 69%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.80 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 7.9 Hz, 2H), (m, 3H), 4.06 (t, J = 6.4 Hz, 2H), 3.69 (t, J = 6.4 Hz, 2H), 3.27 (hept, J = 6.9 Hz, 2H), 2.44 (s, 3H), (m, 2H), 1.71 (p, J = 6.7 Hz, 2H), (m, 2H), 1.42 (m, 2H), 1.21 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 153.3, 144.7, 141.8, 133.2, 129.8, 127.9, 124.4, 123.9, 74.5, 70.5, 30.2, 28.9, 26.4, 25.6, 25.4, 24.1, ESI-HRMS calcd for m/z = [M + H] +, found m/z = DB1 3PF 6 : A mixture of S2 2PF 6 (100 mg, 0.17 mmol) and S3 (100 mg, 0.23 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB1 3PF 6 (100 mg, 60%). 1 H NMR (500 MHz, CD 3 CN): δ (m, 4H), 8.42 (d, J = 6.9 Hz, 2H), (m, 4H), 8.21 (s, 1H), (m, 3H), 4.69 (t, J = 8.0 S5

6 Hz, 2H), 4.65 (t, J = 7.5 Hz, 2H), 4.55 (t, J = 7.5 Hz, 2H), 3.73 (t, J = 6.4 Hz, 2H), 3.30 (hept, J = 6.9 Hz, 2H), 2.65 (p, J = 7.2 Hz, 2H), 2.50 (s, 6H), (m, 2H), (m, 2H), 1.61 (m, 2H), (m, 2H), 1.19 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 153.9, 151.1, 150.3, 147.8, 146.4, 146.2, 142.4, 142.0, 140.1, 128.1, 127.8, 125.1, 124.6, 75.0, 62.7, 58.9, 58.2, 32.2, 31.5, 30.4, 26.8, 26.1, 25.9, 23.9, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S4: A mixture of 2,6-diisopropylphenol (1.78 g, 10 mmol), 8-bromooctan-1-ol (2.2 g, 11 mmol) and K 2 CO 3 (1.5 g, 11 mmol) was stirred at 80 C in DMF (30 ml) overnight. After cooling to room temperature, the mixture was poured into H 2 O (100 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 x 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (100 ml). After drying (MgSO 4 ), the solvent was removed in vacuo to afford a crude precursor as a light-yellow oil. The crude precursor alcohol, p-toluenesulfonyl chloride (2.0 g, 10.5 mmol) and 4-dimethylaminopyridine (122 mg, 1 mmol) were stirred in Et 3 N (5 ml) and CH 2 Cl 2 (50 ml) at room temperature for 3 h. The solution was poured into H 2 O (50 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (50 ml). After drying (MgSO 4 ), the solvent was removed in vacuo and the resulting residue was purified by column chromatography (SiO 2 : Hexanes / EtOAc 5:1) to afford S4 (2.61 g, 57%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.80 (d, J = 8.3 Hz, 2H), 7.35 (d, J = 8.3 Hz, 2H), (m, 3H), 4.04 (t, J = 6.5 Hz, 2H), 3.71 (t, J = 6.6 Hz, 2H), 3.30 (hept, J = 6.9 Hz, 2H), 2.45 (s, 3H), (m, 2H), (m, 2H), (m, 2H), (m, 6H), 1.22 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 153.4, 144.6, 141.8, 133.3, 129.8, 127.9, 124.3, 123.9, 74.8, 70.6, 30.4, 29.3, 28.9, 28.8, 26.4, 26.0, 25.3, 24.1, ESI-HRMS calcd for m/z = [M + H] +, found m/z = S6

7 DB2 3PF 6 : A mixture of S2 2PF 6 (100 mg, 0.17 mmol) and S4 (100 mg, 0.22 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed in vacuum. The resulting residue was purified by column chromatography ((SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB2 3PF 6 (131 mg, 76%). 1 H NMR (500 MHz, CD 3 CN): δ (m, 4H), 8.42 (d, J = 6.0 Hz, 2H), (m, 4H), 8.20 (s, 1H), (m, 3H), 4.71 (t, J = 7.5 Hz, 2H), 4.63 (t, J = 7.3 Hz, 2H), 4.56 (t, J = 7.5 Hz, 2H), 3.72 (t, J = 6.4 Hz, 2H), 3.30 (hept, J = 6.9 Hz, 2H), (m, 2H), 2.50 (s, 6H), (m, 2H), (m, 2H), (m, 2H), (m, 6H), 1.19 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 153.0, 150.1, 149.3, 146.9, 145.5, 145.2, 141.4, 141.1, 139.1, 127.1, 126.9, 124.2, 123.6, 74.2, 61.8, 57.9, 57.3, 31.3, 30.7, 29.7, 28.6, 28.3, 25.8, 25.4, 25.2, 23.0, ESI-HRMS calcd for m/z = S7

8 [M PF 6 ] +, found m/z = S5: A mixture of 2,6-diisopropylphenol (3.56 g, 20 mmol), 11-bromo-1-undecanol (5.1 g, 20 mmol) and K 2 CO 3 (3 g, 22 mmol) was stirred at 80 C in DMF (30 ml) overnight. After cooling to room temperature, the mixture was poured into H 2 O (100 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (100 ml). After drying (MgSO 4 ), the solvent was removed in vacuo to afford a crude precursor as a light-yellow oil. The crude precursor alcohol, p-toluenesulfonyl chloride (4.0 g, 21 mmol) and 4-dimethylaminopyridine (122 mg, 1 mmol) was stirred in Et 3 N (10 ml) and CH 2 Cl 2 (50 ml) at room temperature for 3 h. The solution was poured into H 2 O (50 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (50 ml). After drying (MgSO 4 ), the solvent was removed in vacuo and the resulting residue was purified by column chromatography (SiO 2 : Hexanes / EtOAc 5:1) to afford S5 (6.94 g, 69%). 1 H NMR (500 MHz, CDCl 3 ) 1 H NMR (500 MHz, CDCl 3 ) δ 7.79 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), (m, 3H), 4.02 (t, J = 6.5 Hz, 2H), 3.72 (t, J = 6.6 Hz, 2H), 3.31 (hept, J = 6.9 Hz, 2H), 2.45 (s, 3H), (m, 2H), (m, 2H), (m, 2H), (m, 12H), 1.22 (d, J = 7.1 Hz, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 153.5, 144.6, 141.8, 133.3, 129.8, 127.9, 124.3, 123.9, 74.9, 70.7, 30.4, 29.6, 29.5, 29.5, 29.4, 29.0, 28.9, 26.4, 26.1, 25.4, 24.1, ESI-HRMS calcd for m/z = [M + H] +, found m/z = S8

9 DB3 3PF 6 : A mixture of S2 2PF 6 (100 mg, 0.17 mmol) and S5 (100 mg, 0.20 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB3 3PF 6 (61 mg, 34%). 1 H NMR (500 MHz, CD 3 CN): δ 8.95 (d, J = 5.4 Hz, 2H), 8.93 (d, J = 6.9 Hz, 2H), 8.45 (d, J = 6.9 Hz, 2H), 8.43 (s, 2H), 8.41 (d, J = 6.4 Hz, 2H), 8.23 (s, 1H), (m, 3H), 4.73 (t, J = 8.0 Hz, 2H), 4.64 (t, J = 7.6 Hz, 2H), 4.59 (t, J = 7.5 Hz, 2H), 3.74 (t, J = 6.4 Hz, 2H), 3.34 (hept, J = 6.9 Hz, 2H), (m, 2H), 2.53 (s, 6H), (m, 2H), (m, 2H), 1.54 (p, J = 6.8 Hz, 2H), (m, 12H), S9

10 1.22 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 153.0, 150.1, 149.3, 146.9, 145.5, 145.2, 141.4, 141.1, 139.1, 127.1, 126.8, 124.1, 123.6, 74.2, 61.8, 57.9, 57.3, 31.3, 30.7, 29.7, 29.0, 28.9, 28.8, 28.7, 28.3, 25.8, 25.4, 25.2, 23.0, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = DB4 3PF 6 : A mixture of S2 2PF 6 (100 mg, 0.17 mmol) and S6 2 (100 mg, 0.22 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB4 3PF 6 (101 mg, 58%). 1 H NMR (500 MHz, CD 3 CN): δ 8.99 (d, J = 6.9 Hz, 2H), 8.86 (d, J = 6.4 Hz, 2H), 8.39 (s, 2H), 8.34 (d, J = 6.5 Hz, 2H), 8.29 (d, J = 6.3 Hz, 2H), 8.20 (s, 1H), (m, 3H), 4.80 (t, J = 4.8 Hz, 2H), 4.69 (t, J = 7.6 Hz, 2H), 4.55 (t, J = S10

11 7.5 Hz, 2H), 4.03 (t, J = 4.3 Hz, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), 3.37 (hept, J = 6.9 Hz, 2H), (m, 2H), 2.50 (s, 6H), 1.15 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 153.5, 151.0, 150.4, 147.8, 146.9, 146.3, 142.4, 142.0, 140.0, 128.0, 127.3, 125.4, 124.8, 74.4, 70.9, 70.7, 69.2, 62.2, 58.9, 58.2, 32.3, 26.5, 23.9, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S7: A mixture of 2,6-diisopropylphenol (0.52 g, 2.9 mmol), tetraethylene glycol monotosylate (1.0 g, 2.9 mmol) and K 2 CO 3 (0.7 g, 5 mmol) was stirred at 80 C in DMF (20 ml) overnight. After cooling to room temperature, the mixture was poured into H 2 O (100 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed S11

12 with saturated aqueous NaCl solution (100 ml). After drying (MgSO 4 ), the solvent was removed in vacuo to afford the crude alcohol as a light-yellow oil. This crude precursor alcohol, p-toluenesulfonyl chloride (0.57 g, 3 mmol) and 4-dimethylaminopyridine (20 mg, 0.16 mmol) were stirred in Et 3 N (5 ml) and CH 2 Cl 2 (30 ml) at room temperature for 3 h. The solution was poured into H 2 O (50 ml). The resulting mixture was extracted with CH 2 Cl 2 (3 30 ml) and the combined organic phases were washed with saturated aqueous NaCl solution (50 ml). After drying (MgSO 4 ), the solvent was removed in vacuo and the resulting residue was purified by column chromatography (SiO 2 : Hexanes / EtOAc 1:1) to afford S7 (0.58 g, 40%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.80 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.09 (s, 3H), 4.16 (t, J = 5.0 Hz, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 2H), (m, 2H), 3.37 (hept, J = 6.9 Hz, 2H), 2.44 (s, 3H), 1.21 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 153.0, 144.8, 141.8, 132.9, 129.8, 128.0, 124.6, 124.0, 73.8, 71.0, 70.8, 70.8, 70.7, 70.6, 69.2, 68.7, 26.2, 24.2, ESI-HRMS calcd for m/z = [M + H] +, found m/z = DB5 3PF 6 : A mixture of S2 2PF 6 (100 mg, 0.17 mmol) and S7 (150 mg, 0.29 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB5 3PF 6 (39 mg, 21%). 1 H NMR (500 MHz, CD 3 CN): δ 9.00 (d, J = 7.0 Hz, 2H), 8.91 (d, J = 6.7 Hz, 2H), 8.44 (d, J = 7.0 Hz, 2H), (m, 4H), 8.24 (s, 1H), (m, 3H), 4.81 (t, J = 5.9 Hz, 2H), 4.71 (t, J = 7.6 Hz, 2H), 4.58 (t, J = 7.5 Hz, 2H), 4.03 (t, J = 5.0 Hz, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 4H), 3.39 (hept, J = 6.9 Hz, 2H), (m, 2H), 2.53 (s, 6H), 1.19 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 152.6, 150.2, 149.5, 146.9, 146.0, 145.4, 141.5, 141.1, 139.1, 127.1, S12

13 126.4, 124.5, 123.8, 73.6, 70.1, 70.0, 69.8, 69.8, 69.7, 68.2, 61.3, 57.9, 57.3, 31.3, 25.6, 23.0, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = DB8 3PF 6 : A mixture of S8 2PF 3 6 (100 mg, 0.17 mmol) and S3 (100 mg, 0.23 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB8 3PF 6 (100 mg, 60%). 1 H NMR (500 MHz, CD 3 CN): δ 8.96 (d, J = 6.9 Hz, 2H), 8.90 (d, J = 6.9 Hz, 2H), 8.47 (d, J = 6.9 Hz, 2H), (m, 4H), 8.30 (s, 1H), (m, 3H), 5.20 (t, J = 6.6 Hz, 2H), 5.05 (t, J = 6.6 Hz, 2H), 4.68 (t, J = 7.5 Hz, 2H), 3.76 (t, J = 6.4 Hz, 2H), 3.33 (hept, J = 6.9 Hz, 2H), 2.52 (s, 6H), (m, 2H), (m, 2H), S13

14 (m, 2H), (m, 2H), 1.22 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 154.3, 152.4, 150.5, 149.4, 147.2, 146.7, 142.8, 142.8, 141.0, 128.9, 128.3, 125.6, 125.0, 75.4, 63.2, 60.9, 60.3, 31.9, 30.8, 27.2, 26.6, 26.3, 24.3, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = DB7 3PF 6 : A mixture of S8 2PF 3 6 (100 mg, 0.17 mmol) and S4 (100 mg, 0.22 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB7 3PF 6 (118 mg, 67%). 1 H NMR (500 MHz, CD 3 CN): δ 8.92 (d, J = 6.3 Hz, 2H), 8.82 (d, J = 6.6 Hz, 2H), 8.44 (d, J = 6.4 Hz, 2H), 8.39 (d, J = 6.3 Hz, 2H), 8.36 (s, 2H), 8.27 (s, 1H), (m, 3H), 5.16 (t, J = 6.5 Hz, 2H), 5.01 (t, J = 6.5 Hz, 2H), 4.64 (t, J = S14

15 7.6 Hz, 2H), 3.73 (t, J = 6.4 Hz, 2H), 3.31 (hept, J = 6.9 Hz, 2H), 2.49 (s, 6H), (m, 2H), (m, 2H), (m, 2H), (m, 6H), 1.19 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 154.4, 152.4, 150.5, 149.5, 147.1, 146.7, 142.8, 142.7, 141.0, 128.9, 128.3, 125.5, 125.0, 75.6, 63.2, 60.9, 60.4, 32.0, 31.0, 29.9, 29.6, 27.2, 26.7, 26.6, 24.3, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S10 2PF 6 : A mixture of 3,5-lutidine (1.07 g, 10 mmol) and 1,4-dibromobutane (10 ml) was stirred at 120 C overnight. After cooling to room temperature, the mixture was poured into Et 2 O (50 ml). The resulting suspension was extract with H 2 O (3 20 ml), then NH 4 PF 6 (2 g) was added to the combined water phase. The precipitate was filtered and washed with H 2 O (3 5 ml) to afford S9 PF 6 (3.45 g, 89%). A mixture of S9 PF 6 (3.0 g, 7.7 mmol) and 4,4 -bipyridine (1.0 g, S15

16 6.4 mmol) were stirred in MeCN (10 ml) for 3 days. After cooling to room temperature, the mixture was poured into Et 2 O (50 ml). The resulting suspension was filtered and washed with Et 2 O (3 5 ml). The solid was dissolved in H 2 O (50 ml), then NH 4 PF 6 (2 g) was added. The precipitate was filtered and washed with H 2 O (3 5 ml) to afford a crude product, which was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford S10 2PF 6 (2.07 g, 54%) as a white solid. 1 H NMR (500 MHz, CD 3 CN): δ (m, 2H), 8.77 (d, J = 6.9 Hz, 2H), (m, 4H), 8.18 (d, J = 5.6 Hz, 1H), 7.82 (d, J = 6.2 Hz, 2H), 4.59 (t, J = 5.8 Hz, 2H), 4.47 (t, J = 5.9 Hz, 2H), 2.49 (s, 6H), (m, 4H). 13 C NMR (126 MHz, CD 3 CN): δ 154.0, 150.8, 146.5, 144.6, 140.9, 140.8, 138.8, 125.7, 121.4, 60.1 (2 C), 26.9, 26.7, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S16

17 DB6 3PF 6 : A mixture of S18 2PF 6 (100 mg, 0.17 mmol) and S4 (100 mg, 0.22 mmol) was stirred at 80 C in MeCN (1 ml) for 3 days. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography (SiO 2 : MeOH / NH 4 Cl (aq, 2M) / MeNO 2 = 7:2:1), followed by counterion exchange (NH 4 PF 6 / H 2 O) to afford DB6 3PF 6 (154 mg, 90%). 1 H NMR (500 MHz, CD 3 CN): δ 8.93 (d, J = 7.0 Hz, 2H), 8.91 (d, J = 6.9 Hz, 2H), (m, 4H), 8.38 (s, 2H), 8.19 (t, J = 6.5 Hz, 1H), (m, 3H), (m, 4H), 4.49 (t, J = 6.5 Hz,2H), 3.75 (t, J = 6.4 Hz, 2H), 3.33 (hept, J = 6.9 Hz, 2H), 2.50 (s, 6H), (m, 6H), (m, 2H), (m, 2H), (m, 6H), 1.22 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CD 3 CN): δ 153.0, 149.8, 149.4, 146.5, 145.3, 145.2, 141.4, 141.0, 138.8, 126.9, 126.8, 124.2, 123.6, 74.2, 61.8, 60.7, 60.0, 30.7, 29.7, 28.6, 28.3, 27.0, 26.7, 25.8, 25.4, 25.2, 23.0, ESI-HRMS calcd for m/z = [M PF 6 ] +, found m/z = S11 7PF 6 : DB7 3PF 6 (30 mg, 0.03 mmol) and CBPQT 4PF 6 (35 mg, mmol) were dissolved in MeCN (20 ml, degassed). An excess of activated Zn dust was added to the solution in a glovebox. After stirring for 30 min, the mixture was filtered and NOPF 6 (20 mg, 0.11 mmol) was added. The mixture was analyzed by HPLC-MS before being purified by column chromatography (C 18 -functionalized SiO 2 : H 2 O / MeCN with 0.1% CF 3 COOH). The product containing fractions were combined, an excess of NH 4 PF 6 was added and the organic solvent was evaporated under reduced pressure. The resulting precipitate was collected by filtration, washed with copious amounts H 2 O, and dried under high vacuum to afford S11 7PF 6 (30 mg, 50%) as a colorless solid. 1 H NMR (500 MHz, CD 3 CN): δ (m, 10H), 8.86 (d, J = 6.3 Hz, 2H), (m, 4H), 8.44 (b, 8H), 8.38 (s, 2H), 8.29 (s, 1H), 7.62 (s, 8H), (m, 3H), S17

18 5.84 (dd, J = 22.7, 13.8 Hz, 8H), 5.20 (t, J = 6.4 Hz, 2H), 5.04 (t, J = 6.6 Hz, 2H), 4.63 (t, J = 8.0 Hz, 2H), (m, 4H), 2.51 (s, 6H), (m, 2H), 1.47 (d, J = 7.0 Hz, 12H), 0.57 (b, 2H), 1.24 (b, 2H), 1.45 (b, 2H), 1.68 (b, 4H). 13 C NMR (126 MHz, CD 3 CN): δ 153.0, 152.1, 150.2, 149.1, 148.7, 146.8, (2 C), 142.3, 141.8, 140.7, 136.8, 131.0, 128.6, 128.0, 127.8, 126.0, 125.2, 74.8, 65.3, 62.4, 60.6, 60.0, 31.6, 30.4, 29.8, 29.6, 26.9 (2 C), 26.5, 24.5, ESI-HRMS calcd for m/z = [M 2PF 6 ] 2+, found m/z = Figure S1. Analytical HPLC trace of a) DB7 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedure, b) DB7 3PF 6 and c) CBPQT 4PF 6 S18

19 3. UV/Vis/NIR Spectroscopy DB0 4PF 6 (1.0 mg, mmol) or CBPQT 4PF 6 (1.1 mg, mmol) was dissolved in MeCN (10 ml, degassed). Excess of activated Zn dust was added to it and stirred for 10 min in a glovebox. The solution changed to blue in seconds. The UV/Vis/NIR spectrum was recorded after filtering. A mixture of DB0 4PF 6 (1.0 mg, mmol) and CBPQT 4PF 6 (1.1 mg, mmol) was dissolved in MeCN (10 ml, degassed). Excess of activated Zn dust was added to the mixture and it was stirred for 10 min in a glovebox. The solution changed to blue then purple in seconds. The UV/Vis/NIR spectrum was recorded after filtering. Figure S2. UV/Vis/NIR Spectra of DB0 3+ (black trace), CBPQT 2(+ ) (blue trace), DB0 3+ CBPQT 2(+ ) (purple trace). The broad peak around 1100 nm indicates formation of a trisradical complex 4. [CBPQT 4+ ] = M. [DB0 4+ ] = M. S19

20 4. Single Crystal X-Ray Diffraction Excess of activated zinc dust was added to a mixture of DB0 4PF 6 (1.0 mg, 1.0 µmol) and CBPQT 4PF 6 (1.1 mg, 1.0 µmol) in MeCN (1 ml) in a glovebox, and the mixture was stirred for 30 min. After filtering, the purple solution was kept under an atmosphere of ipr 2 O at 0 C to allow slow vapor diffusion to occur. Single crystals of DB0 CBPQT 6PF 6, an overall bisradical species, were formed after a month. They were immersed in inert oil and transferred to the cold gas stream of a Bruker Kappa APEX CCD area detector, equipped with a CuKα microsource with MX optics. A SADABS-2008/1 (Bruker,2008) was used for absorption correction. wr2(int) was before and after correction. The ratio of minimum to maximum transmission was The λ/2 correction factor is not present. Figure S3. Crystal structure of DB0 CBPQT 6PF 6 a) top view, b) and c) side views, d) space filling representation. Solvent molecules and counter ions are omitted for clarity. S20

21 Crystal Data for C 82 H 94 F 36 N 16 P 6, M = , monoclinic, a = (10), b = (13), c = (8), β = (3), V = (5) Å 3, T = 99.98, space group P21/c (no. 14), Z = 2, µ(cukα) = 2.114, reflections measured, 8210 unique (R int = ) which were used in all calculations. The final wr(f 2 ) was (all data), R 1 = for I > 2σ(I). No special refinement necessary. Crystallographic data (excluding structure factors) for the structures reported in this communication have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC It is worth highlighting that the solid-state structures contains 6 hexafluorophosphate anions, indicating the inclusion complex is not a trisradical complex as we observed by UV/Vis/NIR spectroscopy in solution. Possible reasons for this unexpected phenomenon might be that: (i) the trace amount of oxygen in glovebox (< 10 ppm) oxidized the trisradical specials as the crystals were growing slowly over a month, (ii) both trisradical and bisradical crystals formed, but, the crystal of the trisradical could be not distinguishable from the bisradical (in term of morphology), crystals of C 82 H 94 F 36 N 16 P 6 were chosen for crystallography, or (iii) the bisradical state may crystallize preferentially as has been witnessed previously. 5 Although unexpected, this experimental observation is still in keeping with the formation of the trisradical inclusion complex that we observe spectroscopically in solution H NMR Spectroscopy Investigation of Pumping and Dethreading General procedure for pumping and dethreading experiments: The dumbbell (DB1 3PF 6, DB2 3PF 6, DB3 3PF 6, DB4 3PF 6, DB5 3PF 6, DB6 3PF 6, DB7 3PF 6, or DB8 3PF 6, mmol) and CBPQT 4PF 6 (1.1 mg, mmol) were dissolved in CD 3 CN (0.75 ml, degassed). Excess of Zn dust was added to the solution in a glovebox. The solution changes quickly to a deep blue color and then to purple in seconds. After stirring for 5 min, the mixture is filtered and tris(4-bromophenyl)aminium hexachloridoantimonate (Magic Blue)(5 mg, mmol) is added at 0 C, causing the solution to change color quickly to deep blue. The resulting solution is sealed in an NMR tube and analyzed by 1 H NMR spectroscopy. S21

22 Figure S4. 1 H NMR Spectra (recorded in CD 3 CN) of a) DB1 3PF 6, b) DB1 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 4 h at 6 C, and d) CBPQT 4PF 6. e) 1 H NMR Spectra recorded at 6 C over 4 h. (f) The change in the molar ratio with time based on 1 H NMR integration. The inset shows a linear relationship between ln(c/c 0 ) and time, indicating that the dethreading obeys first order kinetics. The activation barrier G was calculated using the Eyring equation. S22

23 Figure S5. 1 H NMR spectra (recorded in CD 3 CN) of a) DB2 3PF 6, b) DB2 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 3 h at 58 C, and d) CBPQT 4PF 6. e) 1 H NMR Spectra recorded at 58 C over 3 h. (f) The change in the molar ratio with time based on 1 H NMR integration. The inset shows a linear relationship between ln(c/c 0 ) and time, indicating that the dethreading obeys first order kinetics. The activation barrier G was calculated using the Eyring equation. S23

24 Figure S6. 1 H NMR Spectra (recorded in CD 3 CN) of a) DB3 3PF 6, b) DB3 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 14 h at 92 C, and d) CBPQT 4PF 6. e) 1 H NMR Spectra recorded at 92 C over 14 h. (f) The change in the molar ratio with time based on 1 H NMR integration. The inset shows a linear relationship between ln(c/c 0 ) and time, indicating that the dethreading obeys first order kinetics. The activation barrier G was calculated using the Eyring equation. S24

25 Figure S7. 1 H NMR Spectra (recorded in CD 3 CN) of a) DB4 3PF 6, b) DB4 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 6 h at 44 C, and d) CBPQT 4PF 6. e) 1 H NMR Spectra recorded at 44 C over 6 h. (f) The change in the molar ratio with time based on 1 H NMR integration. The inset shows a linear relationship between ln(c/c 0 ) and time, indicating that the dethreading obeys first order kinetics. The activation barrier G was calculated using the Eyring equation. S25

26 Figure S8. 1 H NMR spectra (recorded in CD 3 CN) of a) DB5 3PF 6, b) DB5 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 10 h at 82 C, and d) CBPQT 4PF 6. e) 1 H NMR Spectra recorded at 82 C over 10 h. (f) The change in the molar ratio with time based on 1 H NMR integration; the S shape curve indicating the dethreading is indicative of an auto-catalytic process. S26

27 Figure S9. 1 H NMR Spectra (CD 3 CN, 298 K) of a) DB6 3PF 6, b) DB6 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) CBPQT 4PF 6. No obvious shifts were identified indicating that the spectrum b) is a simple physical mixture of DB6 3PF 6 and CBPQT 4PF 6 S27

28 Figure S10. 1 H NMR Spectra (recorded in CD 3 CN) of a) DB7 3PF 6, b) DB7 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 18 h at 82 C, and d) CBPQT 4PF 6. The spectrum of the mixture of DB7 3PF 6 and CBPQT 4PF 6 after the reduction and oxidation procedure does not change at high temperature over several hours (cf. b and c) indicating the dethreading barrier for CBPQT 4+ is high. Additional peaks in aromatic area are attributed to the decomposition of Magic Blue upon subjecting to high temperature over an extended period of time. S28

29 Figure S11. 1 H NMR Spectra (recorded in CD 3 CN) of a) DB8 3PF 6, b) DB8 3PF 6 and CBPQT 4PF 6 immediately after the reduction and oxidation procedures, and c) after 16 h at 82 C, d) CBPQT 4PF 6. e) 1 H NMR Spectra recorded at 82 C over 16 h. (f) The change in the molar ratio with time based on 1 H NMR integration. The inset shows a linear relationship between ln(c/c 0 ) and time, indicating that the dethreading obeys first order kinetics. The activation barrier G was calculated using the Eyring equation. S29

30 Table S1. Summary of Thermodynamic Data. Compound Dethreading rate constant k / 10-5 s -1 (Temperature / K) Activation barrier a G / kcal mol -1 Half life time b t 1/2 at 298 K / h DB1 3PF ± 0.6 (279) DB2 3PF 6 12 ± 1 (331) DB3 3PF ± 0.2 (365) DB4 3PF ± 0.2 (317) DB5 3PF DB6 3PF 6 > 1000 (298) < 18.3 < 0.01 DB7 3PF 6 < 0.05 (355) > 31.3 > DB8 3PF ± 0.1 (355) a Calculated using the Erying equation using the detheading rate constant. b Calculated using t 1/2 = ln2 / k 298K, where k 298K is the dethreading rate constant at 298 K where can be obtained using the Eyring equation with G, assuming the temperature dependence of G can be ignored. Table S2. Summary of Rotaxane Yield at Different Oxidization Temperatures. a Dumbbell Yield (%) RT 0 o C 40 o C DB7 3PF DB2 3PF >95 DB6 3PF <5 a Dumbell (1.0 mg, mmol) and CBPQT 4PF 6 (1.1 mg, mmol) was dissolved in CD 3 CN (0.75 ml, degassed). Excess of Zn dust was added to the solution in a glovebox. After stirring for 5 min, the mixture was filtered and tris(4-bromophenyl)aminium hexachloridoantimonate (Magic Blue, 5 mg, mmol) was added at the given temperature before the sample was analyzed by 1 H NMR at that temperature. S30

31 6. DFT calculations The geometries were optimized using the PBF Poisson-Boltzmann solvation model 6 for acetonitrile (ɛ=37.5 and R 0 = 2.18 Å) at the level of M06-HF/6-31G* with Jaguar The single point was refined at the level of M06-HF/ G**. We assumed that two MeCN molecules are contained in the cavity of free CBPQT 4+ in solution. The energies of DB1 3+, DB2 3+, DB3 3+ and corresponding CBPQT 4+ rotaxanes are listed in Table S3. In order to obtain the potential profile for the dethreading process for DB8 3+ and DB9 3+, the center of the CBPQT 4+ ring was scanned along each atom of the molecule. Various numbers of chloride anions (0 3) were placed around the molecule as counterions to accommodate better the change of electrostatics as a result of the motion of CBPQT 4+ ring. Then the minimum was evaluated for each point along the potential profile. The barrier was calculated as the difference between the highest point in the potential profile and the rotaxane with CBPQT 4+ optimized with no constraint at the end of diisopropylphenol (defined as freely optimized in the Table S4 and S11). The total is the sum of refined single point and solvation, as provided in the Table S4 13. The gas phase is the DFT for a vacuum with no corrections for zero-point (ZPE). The solution phase includes the solute and half of the solute-solvent. The solvation is the difference between these two quantities. The refined single point is the DFT for a vacuum at G** level. The difference between refined single point in column 5 and gas phase in column 3 is subtracted from solution phase in column 2 to give the total in column 6. This total does not include the effects of entropy and specific heat needed to get the free at the S31

32 temperature of the experiments. The total is the quantity to be used in considering the profiles. Table S3. The components of DB1 3+, DB2 3+, DB3 3+, CBPQT 4+ and corresponding [2]pseudorotaxanes. solution phase gas phase solvation refined single point total DB DB DB DB1 3+ CBPQT DB2 3+ CBPQT DB3 3+ CBPQT CBPQT CH 3 CN CBPQT CH 3 CN S32

33 Table S4. The components of CBPQT 4+ moving on DB8 3+ with no Cl. solution phase gas phase solvation refined single point total DB Freely optimized C C C N C C C C C C N C C S33

34 N C C Table S5. The components of CBPQT 4+ moving on DB8 3+ with 1 Cl (configuration 1) solution phase gas phase solvation refined single point total Cl C C C N C C C C C C N C C S34

35 N C C Table S6. The components of CBPQT 4+ moving on DB8 3+ with 1 Cl.(configuration 2) solution phase gas phase solvation refined single point total C C C N C C C C C C N C S35

36 C N C C Table S7. The components of CBPQT 4+ moving on DB8 3+ with 2 Cl (configuration 1) solution phase gas phase solvation refined single point total C C C N C C C C C C N C S36

37 C N C C Table S8. The components of CBPQT 4+ moving on DB8 3+ with 2 Cl (configuration 2) solution phase gas phase solvation refined single point total C C C N C C C C C C N C S37

38 C N C C Table S9. The components of CBPQT 4+ moving on DB8 3+ with 3 Cl (configuration 1) solution phase gas phase solvation refined single point total C C C N C C C C C C N C S38

39 C N C C Table S10. The components of CBPQT 4+ moving on DB8 3+ with 3 Cl (configuration 2) solution phase gas phase solvation refined single point total C C C N C C C C C C N C S39

40 C N C C Figure S12. The potential surface of CBPQT 4+ moving on DB8 3+. These energies are enthalpies at 0K, except that we do not include zero point (the solvation correction is a free at 300K). The reference is at infinite separation. The of S40

41 the rotaxane with CBPQT 4+ optimized with no constraint at the end of diisopropylphenol is 14.4 kcal/mol, leading to the dethreading enthalpic barrier 18.7 kcal/mol. This can be compared to experimental dethreading free barrier of 28.5 kcal mol -1 for DB8 3+ CBPQT 4+. The discrepancy probably arises because the theory does not include ZPE or entropic affects. S41

42 Table S11. The components of CBPQT 4+ moving on DB9 3+ with no Cl solution phase gas phase solvation refined single point total DB freely optimized C C C N C C C C C C N C C C C N C C C S42

43 Table S12. The components of CBPQT 4+ moving on DB9 3+ with 1 Cl (configuration 1) solution phase gas phase solvation refined single point total C C C N C C C C C C N C C C C N C C C S43

44 Table S13. The components of CBPQT 4+ moving on DB9 3+ with 1 Cl (configuration 2) solution phase gas phase solvation refined single point total C C C N C C C C C C N C C C C N C C C S44

45 Table S14. The components of CBPQT 4+ moving on DB9 3+ with 2 Cl (configuration 1) solution phase gas phase solvation refined single point total C C C N C C C C C C N C C C C N C C C S45

46 Table S15. The components of CBPQT 4+ moving on DB9 3+ with 2 Cl (configuration 2) solution phase gas phase solvation refined single point total C C C N C C C C C C N C C C C N C C C S46