A universal diazide-terminated polyether, incorporating tetrathiafulvalene (TTF, green) and 1,5-dioxynaphthalene (DNP, red) units, was prepared and subsequently employed in the template-directed synthesis of a switchable donor/acceptor [2]rotaxane. The triazole rings (magenta), which are introduced into the rotaxane during requisite click reactions, do not present themselves as competing recognition sites for the tetracationic cyclophane (blue) as it is induced to switch between the TTF unit, when it becomes dicationic (green adorned with yellow extremities), and the DNP unit

Aprahamian, Ivan

Dichtel, William R.

Heath, James R.

Ikeda, Taichi

Stoddart, J. Fraser

Caltech Authors - Main

ORGANIC LETTERS 
A Clicked Bistable [2]Rotaxane 
 
Ivan Aprahamian,† William R. Dichtel,†,‡ Taichi Ikeda,† James R. Heath*,‡ and   
J. Fraser Stoddart*,† 
 
California NanoSystems Institute and Department of Chemistry and Biochemistry, 
University of California, Los Angeles 405 Hilgard Avenue Los Angeles, CA, 90095, and Division 
of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena CA 91125 
 
 
 
Supplementary Information 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
                                                 
† CNSI/UCLA 
‡ Caltech 
Correspondence Address 
Prof. Dr. J Fraser Stoddart 
Department of Chemistry and Biochemistry 
University of California, Los Angeles 
405 Hilgard Avenue, Los Angeles, CA 90095-1569 
UNITED STATES OF AMERICA 
Tel: (+1)-310-206-7078 
Fax: (+1)-310-206-5621 
E-Mail: stoddart@chem.ucla.edu 
 S2
Experimental Section 
 
 
General: All reagents and starting materials were purchased from Aldrich and used 
without further purification. Cyclobis(paraquat-p-phenylene) tetrakis(hexafluoro- 
phosphate)S 1  (CBPQT·4PF6), 5-(2-(2-(tetrahydro-2H-pran-2-yloxy)ethoxy)ethoxynaph- 
thalene-1-olS2   (2), the monotosylated tetrathiafulvalene derivativeS3 3 and 4-[bis[4-(t-
butyl)phenyl][4-(isopropyl)phenyl]methyl]phenyl propargyl etherS 4  (6) were prepared 
according to literature procedures. Thin layer chromatography (TLC) was performed on 
silica gel 60 F254 (E. Merck). Column chromatography was performed on silica gel 60F 
(Merck 9385, 0.040–0.063 mm). Melting points were recorded on an Electrothermal 9100 
instrument in open capillary tubes and are uncorrected. Deuterated solvents (Cambridge 
Isotope Laboratories) for NMR spectroscopic analyses were used as received. NMR 
spectra were recorded on Bruker Avance 500 and 600 spectrometers, with working 
frequencies of 500.13 and 600.13 MHz for 1H nuclei, and 125.70 and 150.90 MHz for 
13C nuclei, respectively. Chemical shifts are quoted in ppm relative to tetramethylsilane, 
using the residual solvent peak as a reference standard.  High resolution fast atom 
bombardment (HR-FAB) mass spectra were obtained on a JEOL JMS-600H high 
resolution mass spectrometer equipped with a FAB probe. Electrospray ionization (ESI) 
mass spectra were measured on an IonSpec FT-ICR mass spectrometer. Electrochemical 
and spectroelectrochemical experiments were carried out at room temperature in argon-
purged MeCN solutions, with a Princeton Applied Research 263A Multipurpose 
instrument interfaced to a PC. Cyclic voltammetry experiments were performed using a 
glassy carbon working electrode (0.018 cm2, Cypress Systems). Its surface was polished 
 S3
routinely with 0.05 μm alumina-water slurry on a felt surface immediately before use. 
The counter electrode was a Pt coil and the reference electrode was a standard calomel 
electrode (SCE). The concentration of the sample and supporting electrolyte 
[tetrabutylammonium hexafluorophosphate (TBA•PF6)] were 0.5 mM and 0.1 M, 
respectively. The scan rate was set to 200 mVs-1. In the differential pulse voltammetry 
(DPV) experiment, the pulse height, pulse width, step height and step time were set to 50 
mV, 50 ms, 5 mV, 500 ms, respectively. The peak top potentials for the overlapped peaks 
were determined by using the curve-fitting operation of the IGOR Pro software (Version 
5.04B, Wavemetrix, Inc.). Spectroelectrochemical experiments were made in a custom-
built optically-transparent thin layer electrochemical (OTTLE) cell with an optical path of 
1 mm, using a Pt grid as working electrode, a Pt wire as counter electrode and a Ag wire 
pseudo-reference electrode. Experimental errors: potential values, +/– 10 mV; absorption 
maxima, +/– 2 nm. The scan rate was set to 0.25 mV s-1 and the UV-Vis spectra were 
recorded every two minutes. 
 
Synthesis  
Scheme S1. Synthesis of the DNP/TTF-containing diol derivative 4   
 
 
 
 
 
 
 
 
 
 
 
 S4
4: A solution of 5-(2-(2-(tetrahydro-2H-pran-2-yloxy)ethoxy)ethoxynaphthalen-1-olS2 (2) 
(62 mg, 0.18 mmol), the TTF-monotosylateS3 3 (100 mg, 0.17 mmol), K2CO3 (92 mg, 
0.68 mmol), and [18]crown-6 (5 mg) in dry MeCN (30 mL) was heated under reflux for 
16 h. After cooling down to room temperature, the reaction mixture was filtered and the 
residue was washed with MeCN (20 mL). The combined organic solution was evaporated 
in vacuo to obtain the crude THP-protected compound as a yellow oil, which was re-
dissolved in MeOH / CH2Cl2 (1:1, 100 mL). A conc. HCl aqueous solution (0.5 mL) was 
added and the reaction mixture was stirred at room temperature for 1h. 1N NaOH 
aqueous solution (100 mL) was added to the reaction mixture and it was extracted by 
CH2Cl2 (3 x 100 mL) and dried (MgSO4). After removal of the solvent, the residue was 
purified by column chromatography (SiO2: CH2Cl2/EtOH 99:1) to give the diol 4 (68 mg, 
60%) as a yellow oil; 1H NMR (500 MHz, CD2Cl2): δ = 7.88 (dd, J  = 7.6 Hz, 2H), 7.41 
(dd, J  = 7.6 Hz, 2H), 6.91 (d, J = 7.6 Hz, 2H), 6.28, 6.26, 6.24, 6.23 (4×s, 2H), 4.34−4.29 
(m, 8H), 4.02−4.01 (m, 4H), 3.76−3.59 (m, H16); 13C NMR (125 MHz, CD2Cl2): δ = 
154.8, 154.7, 135.1, 135.0, 134.9, 134.8, 127.1, 127.0, 125.6, 125.5, 116.9, 116.7, 116.6, 
116.5, 114.9, 114.6, 106.1, 73.1, 72.9, 71.3, 70.6, 70.2, 70.1, 69.9, 69.9, 69.8, 68.5, 68.4, 
68.43, 68.4, 68.3, 62.1, 62.0 (x 2);S5 HRMS (FAB): m/z calcd for C30H38O9S4: 670.1398; 
found: 670.1407. 
 
S1: A solution of TsCl (102 mg, 0.54 mmol) in CH2Cl2 (2 mL) was added dropwise to a 
solution of the diol (4) (90 mg, 0.13 mmol), Et3N (0.15 mL, 1.04 mmol) and DMAP (5 
mg) in CH2Cl2 (20 mL) at 0 oC. The reaction mixture was then stirred for 16h at room 
temperature. 
 
 S5
Scheme S2. Synthesis of the DNP/TTF-containing ditosylate S1 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
After removal of the solvent, the residue was purified by column chromatography (SiO2 
CH2Cl2/EtOH 99:1) to give the ditosylate S1 (73 mg, 71%) as a yellow oil; 1H NMR (500 
MHz, CD2Cl2): δ = 7.84 (d, J = 8.1 Hz, 1H), 7.79−7.74 (m, 5H), 7.35 (s, 4H), 7.27 (d, J = 
7.3 Hz, 2H), 6.86 (d, J = 7.2 Hz, 1H), 6.82 (d, J = 7.2 Hz, 1H), 6.20 (s, 2H), 4.28 (br, 4H), 
4.20 (br, 6H), 4.11 (br, 2H), 3.96 (br, 2H), 3.89 (br, 2H), 3.79 (br, 2H), 3.76 (br, 2H), 
3.64 (br, 4H), 3.52 (br, 4H), 2.43 (s, 3H), 2.36 (s, 3H); 13C NMR (125 MHz, CD2Cl2): δ = 
154.8, 154.6, 145.5, 145.4, 135.1, 135.0, 134.9, 134.8, 133.2, 130.3, 130.2, 128.2, 128.2, 
127.1, 127.0, 125.6, 125.6, 116.8, 116.7, 116.4, 116.6, 114.8, 114.7, 110.9, 110.7, 106.0, 
106.1, 71.3, 71.0, 70.2, 70.1, 70.0, 69.9, 69.8, 69.7, 69.3, 69.0, 68.5 (x 2), 68.5, 68.4, 68.3, 
21.8, 21.7;S5 HRMS (FAB): m/z calcd for C44H51O13S6: 978.1576; found: 978.1589. 
 
 
 S6
Scheme S3. Synthesis of the DNP/TTF-containing diazide 5 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
5: A solution of ditosylate S1 (93 mg, 0.09 mmol), and NaN3 (48 mg, 0.72 mmol) in dry 
DMF (10 mL) was heated at 80 °C for 1 d. After removal of the solvent, the residue was 
dissolved in CH2Cl2 (50 mL) and then washed with a saturated aqueous solution of 
NH4Cl (2 x 30 mL) followed by a saturated aqueous solution of K2CO3 (30 mL) followed 
by drying (MgSO4). The crude product, obtained after the removal of the solvent, was 
purified by column chromatography (SiO2: CH2Cl2/EtOH 99:1) to give the diazide 5 (68 
mg, 60%) as a yellow oil; 1H NMR (500 MHz, CD2Cl2): δ = 7.84 (d, J = 8.4 Hz, 2H), 
7.36 (dd, J = 7.7 Hz, 2H), 6.87 (d, J = 7.5 Hz, 2H), 6.23, 6.22, 6.20 (3×s, 4H), 4.28 (m, 
8H), 3.98 (m, 4H), 3.77 (m, 4H), 3.62 (m, 8H), 3.40 (m, 4H); 13C NMR (125 MHz, 
CD2Cl2): δ = 154.8, 154.7, 135.0, 127.1, 125.6, 116.7, 116.6, 116.5, 114.8, 114.7, 110.7, 
106.1, 106.1, 71.3, 70.9, 70.7, 70.4, 70.2, 69.9, 69.89, 68.6, 68.4, 51.3, 51.2;[S5] HRMS 
(FAB): m/z calcd for C30H36N6O7S4: 720.1528; found: 720.1550. 
 S7
Scheme S4. Synthesis of the bistable [2]rotaxane 1·4PF6 
 
 
 
 
 
 
 
 
 
 
 
 
1·4PF6: The TTF/DNP-containing diazide 5 (9.7 mg, 0.013 mmol), CBPQT·4PF6 (15.5 
mg, 0.014 mmol), and the alkyne-functionalized stopper4 7 (14.9 mg, 0.028 mmol) were 
dissolved in DMF (0.18 mL) at room temperature to afford a deep green solution. Stock 
solutions of CuSO4·5H2O in DMF (20 μL, 0.006M) and ascorbic acid in DMF (20 μL, 
0.012M) were added. The solution was stirred at room temperature for 48 h. The crude 
product, obtained after the removal of the solvent, was purified by column 
chromatography (SiO2: Me2CO followed by a 1% w/v NH4PF6 solution in Me2CO). The 
green compound present in this salt solution was concentrated into a small volume and 
the pure product was precipitated from this concentrate following the addition of an 
excess of cold water. The bistable [2]rotaxane 1·4PF6 was isolated as a green solid (23 
mg, 60% yield, mp 150 ºC with decomposition); 1H NMR (600 MHz, CD3CN): δ = 
 S8
8.86−8.79 (m 12H), 8.66 (s, 2H), 8.63 (s, 2H), 7.93 (s, 1H), 7.69 (s, 3H), 7.78 (br, 2H), 
7.69−7.46 (m, 30H), 7.38−7.33 (m, 5H), 7.25 (br, 12H), 7.12 (br, 45H), 6.97−6.92 (m, 
3H), 6.85−6.77 (m, 8H), 6.76 (d, J = 7.6 Hz, 1H), 6.68 (d, J = 7.6 Hz, 1H), 6.42 (d, J = 
7.2 Hz, 2H), 6.14 (s, 1H), 6.03 (s, 2H), 5.87 (s, 1H), 5.66−5.58 (m, 6H), 5.49−5.38 (m, 
12H), 5.04 (s, 2H), 5.03 (s, 2H), 5.01 (s, 2H), 4.99 (s, 2H), 4.61−4.57 (m, 8H), 4.33 (br, 
4H), 4.25 (br, 4H), 4.11 (s, 2H), 4.09 (br 4H), 4.06 (br, 6H), 4.00−3.95 (m, 12H), 3.90 (br, 
6H), 3.84 (br, 4H), 3.79 (br, 6H), 3.74 (br, 2H), 3.71 (br, 2H), 3.61 (br, 2H), 2.83 (hextet, 
J = 6.9 Hz, 4H), 1.25 (br, H72), 1.18−1.16 (m, 24H); MS (ESI): m/z = 1294 [M – 2PF6]2+, 
814 [M – 3PF6]3+, 574 [M – 4PF6]4+; HRMS (FAB): m/z calcd for C144H156F12N10O9P2S4: 
1294.0130; found: 1294.0108 [M – 2PF6]2+. 
 
NMR Spectra of New Compounds 
Figure 1. 1H NMR spectrum of the diol derivative 4   
 
 
 
 
 
 
 
 
 
δ 
 S9
Figure 2. 13C NMR spectrum of the diol derivative 4   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure 3. 1H NMR spectrum of the ditosyl derivative S1 
   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
δ 
δ 
 
Figure 4. 13C NMR spectrum of the diol derivative S1 
   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
δ 
δ 
 S11
Figure 5. 1H NMR spectrum of the ditosyl derivative 5 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure 6. 13 C NMR spectrum of the ditosyl derivative 5 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
δ 
δ 
 S12
Figure 7. 1H NMR spectrum of the rotaxane 1·4PF6 
 
 
 
 
 
 
 
 
 
 
 
Figure 8. COSY spectrum of the rotaxane 1·4PF6 
 
 
 
 
 
 
 
 
 
 
 
δ 
    δ 
 S13
Figure 9. NOESY spectrum of the rotaxane 1·4PF6 
 
 
                                                             
 
(S1) Asakawa, M.; Dehaen, W.; L'abbé, G.; Menzer, S.; Nouwen, J.; Raymo, F. M.; 
Stoddart, J. F.; Williams, D. J. J. Org. Chem. 1996, 61, 9591–9595. 
(S2)   Yamamoto, T.; Tseng, H.-R.; Stoddart, J. F.; Balzani, V.; Credi, A.; Marchioni, F.; 
Venturi, M. Collect. Czech. Chem. Commun. 2003, 68, 1488–1514. 
(S3)   Tseng, H.-R.; Vignon, S. A.; Celestre, P. C.; Perkins, J.; Jeppesen, J. O.; Di Fabio, 
A.; Ballardini, R.; Gandolfi, M. T.; Venturi, M.; Balzani, V.;  Stoddart, J. F. Chem. 
Eur. J. 2004, 10, 155–172  
(S4)  Dichtel, W. R.; Miljanić, O. Š.; Spruell, J. M.; Heath, J. R.; Stoddart, J. F. J. Am. 
Chem. Soc. 2006, 128, 10388–10390. 
(S5) Some of the signals in the 13C NMR spectrum are duplicated because of the     
cis/trans isomerism.    
    δ 


English

A Clicked Bistable [2]Rotaxane

ORGANIC LETTERS 
A Clicked Bistable [2]Rotaxane 
 
Ivan Aprahamian,† William R. Dichtel,†,‡ Taichi Ikeda,† James R. Heath*,‡ and   
J. Fraser Stoddart*,† 
 
California NanoSystems Institute and Department of Chemistry and Biochemistry, 
University of California, Los Angeles 405 Hilgard Avenue Los Angeles, CA, 90095, and Division 
of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena CA 91125 
 
 
 
Supplementary Information 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
                                                 
† CNSI/UCLA 
‡ Caltech 
Correspondence Address 
Prof. Dr. J Fraser Stoddart 
Department of Chemistry and Biochemistry 
University of California, Los Angeles 
405 Hilgard Avenue, Los Angeles, CA 90095-1569 
UNITED STATES OF AMERICA 
Tel: (+1)-310-206-7078 
Fax: (+1)-310-206-5621 
E-Mail: stoddart@chem.ucla.edu 
 S2
Experimental Section 
 
 
General: All reagents and starting materials were purchased from Aldrich and used 
without further purification. Cyclobis(paraquat-p-phenylene) tetrakis(hexafluoro- 
phosphate)S 1  (CBPQT·4PF6), 5-(2-(2-(tetrahydro-2H-pran-2-yloxy)ethoxy)ethoxynaph- 
thalene-1-olS2   (2), the monotosylated tetrathiafulvalene derivativeS3 3 and 4-[bis[4-(t-
butyl)phenyl][4-(isopropyl)phenyl]methyl]phenyl propargyl etherS 4  (6) were prepared 
according to literature procedures. Thin layer chromatography (TLC) was performed on 
silica gel 60 F254 (E. Merck). Column chromatography was performed on silica gel 60F 
(Merck 9385, 0.040–0.063 mm). Melting points were recorded on an Electrothermal 9100 
instrument in open capillary tubes and are uncorrected. Deuterated solvents (Cambridge 
Isotope Laboratories) for NMR spectroscopic analyses were used as received. NMR 
spectra were recorded on Bruker Avance 500 and 600 spectrometers, with working 
frequencies of 500.13 and 600.13 MHz for 1H nuclei, and 125.70 and 150.90 MHz for 
13C nuclei, respectively. Chemical shifts are quoted in ppm relative to tetramethylsilane, 
using the residual solvent peak as a reference standard.  High resolution fast atom 
bombardment (HR-FAB) mass spectra were obtained on a JEOL JMS-600H high 
resolution mass spectrometer equipped with a FAB probe. Electrospray ionization (ESI) 
mass spectra were measured on an IonSpec FT-ICR mass spectrometer. Electrochemical 
and spectroelectrochemical experiments were carried out at room temperature in argon-
purged MeCN solutions, with a Princeton Applied Research 263A Multipurpose 
instrument interfaced to a PC. Cyclic voltammetry experiments were performed using a 
glassy carbon working electrode (0.018 cm2, Cypress Systems). Its surface was polished 
 S3
routinely with 0.05 μm alumina-water slurry on a felt surface immediately before use. 
The counter electrode was a Pt coil and the reference electrode was a standard calomel 
electrode (SCE). The concentration of the sample and supporting electrolyte 
[tetrabutylammonium hexafluorophosphate (TBA•PF6)] were 0.5 mM and 0.1 M, 
respectively. The scan rate was set to 200 mVs-1. In the differential pulse voltammetry 
(DPV) experiment, the pulse height, pulse width, step height and step time were set to 50 
mV, 50 ms, 5 mV, 500 ms, respectively. The peak top potentials for the overlapped peaks 
were determined by using the curve-fitting operation of the IGOR Pro software (Version 
5.04B, Wavemetrix, Inc.). Spectroelectrochemical experiments were made in a custom-
built optically-transparent thin layer electrochemical (OTTLE) cell with an optical path of 
1 mm, using a Pt grid as working electrode, a Pt wire as counter electrode and a Ag wire 
pseudo-reference electrode. Experimental errors: potential values, +/– 10 mV; absorption 
maxima, +/– 2 nm. The scan rate was set to 0.25 mV s-1 and the UV-Vis spectra were 
recorded every two minutes. 
 
Synthesis  
Scheme S1. Synthesis of the DNP/TTF-containing diol derivative 4   
 
 
 
 
 
 
 
 
 
 
 
 S4
4: A solution of 5-(2-(2-(tetrahydro-2H-pran-2-yloxy)ethoxy)ethoxynaphthalen-1-olS2 (2) 
(62 mg, 0.18 mmol), the TTF-monotosylateS3 3 (100 mg, 0.17 mmol), K2CO3 (92 mg, 
0.68 mmol), and [18]crown-6 (5 mg) in dry MeCN (30 mL) was heated under reflux for 
16 h. After cooling down to room temperature, the reaction mixture was filtered and the 
residue was washed with MeCN (20 mL). The combined organic solution was evaporated 
in vacuo to obtain the crude THP-protected compound as a yellow oil, which was re-
dissolved in MeOH / CH2Cl2 (1:1, 100 mL). A conc. HCl aqueous solution (0.5 mL) was 
added and the reaction mixture was stirred at room temperature for 1h. 1N NaOH 
aqueous solution (100 mL) was added to the reaction mixture and it was extracted by 
CH2Cl2 (3 x 100 mL) and dried (MgSO4). After removal of the solvent, the residue was 
purified by column chromatography (SiO2: CH2Cl2/EtOH 99:1) to give the diol 4 (68 mg, 
60%) as a yellow oil; 1H NMR (500 MHz, CD2Cl2): δ = 7.88 (dd, J  = 7.6 Hz, 2H), 7.41 
(dd, J  = 7.6 Hz, 2H), 6.91 (d, J = 7.6 Hz, 2H), 6.28, 6.26, 6.24, 6.23 (4×s, 2H), 4.34−4.29 
(m, 8H), 4.02−4.01 (m, 4H), 3.76−3.59 (m, H16); 13C NMR (125 MHz, CD2Cl2): δ = 
154.8, 154.7, 135.1, 135.0, 134.9, 134.8, 127.1, 127.0, 125.6, 125.5, 116.9, 116.7, 116.6, 
116.5, 114.9, 114.6, 106.1, 73.1, 72.9, 71.3, 70.6, 70.2, 70.1, 69.9, 69.9, 69.8, 68.5, 68.4, 
68.43, 68.4, 68.3, 62.1, 62.0 (x 2);S5 HRMS (FAB): m/z calcd for C30H38O9S4: 670.1398; 
found: 670.1407. 
 
S1: A solution of TsCl (102 mg, 0.54 mmol) in CH2Cl2 (2 mL) was added dropwise to a 
solution of the diol (4) (90 mg, 0.13 mmol), Et3N (0.15 mL, 1.04 mmol) and DMAP (5 
mg) in CH2Cl2 (20 mL) at 0 oC. The reaction mixture was then stirred for 16h at room 
temperature. 
 
 S5
Scheme S2. Synthesis of the DNP/TTF-containing ditosylate S1 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
After removal of the solvent, the residue was purified by column chromatography (SiO2 
CH2Cl2/EtOH 99:1) to give the ditosylate S1 (73 mg, 71%) as a yellow oil; 1H NMR (500 
MHz, CD2Cl2): δ = 7.84 (d, J = 8.1 Hz, 1H), 7.79−7.74 (m, 5H), 7.35 (s, 4H), 7.27 (d, J = 
7.3 Hz, 2H), 6.86 (d, J = 7.2 Hz, 1H), 6.82 (d, J = 7.2 Hz, 1H), 6.20 (s, 2H), 4.28 (br, 4H), 
4.20 (br, 6H), 4.11 (br, 2H), 3.96 (br, 2H), 3.89 (br, 2H), 3.79 (br, 2H), 3.76 (br, 2H), 
3.64 (br, 4H), 3.52 (br, 4H), 2.43 (s, 3H), 2.36 (s, 3H); 13C NMR (125 MHz, CD2Cl2): δ = 
154.8, 154.6, 145.5, 145.4, 135.1, 135.0, 134.9, 134.8, 133.2, 130.3, 130.2, 128.2, 128.2, 
127.1, 127.0, 125.6, 125.6, 116.8, 116.7, 116.4, 116.6, 114.8, 114.7, 110.9, 110.7, 106.0, 
106.1, 71.3, 71.0, 70.2, 70.1, 70.0, 69.9, 69.8, 69.7, 69.3, 69.0, 68.5 (x 2), 68.5, 68.4, 68.3, 
21.8, 21.7;S5 HRMS (FAB): m/z calcd for C44H51O13S6: 978.1576; found: 978.1589. 
 
 
 S6
Scheme S3. Synthesis of the DNP/TTF-containing diazide 5 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
5: A solution of ditosylate S1 (93 mg, 0.09 mmol), and NaN3 (48 mg, 0.72 mmol) in dry 
DMF (10 mL) was heated at 80 °C for 1 d. After removal of the solvent, the residue was 
dissolved in CH2Cl2 (50 mL) and then washed with a saturated aqueous solution of 
NH4Cl (2 x 30 mL) followed by a saturated aqueous solution of K2CO3 (30 mL) followed 
by drying (MgSO4). The crude product, obtained after the removal of the solvent, was 
purified by column chromatography (SiO2: CH2Cl2/EtOH 99:1) to give the diazide 5 (68 
mg, 60%) as a yellow oil; 1H NMR (500 MHz, CD2Cl2): δ = 7.84 (d, J = 8.4 Hz, 2H), 
7.36 (dd, J = 7.7 Hz, 2H), 6.87 (d, J = 7.5 Hz, 2H), 6.23, 6.22, 6.20 (3×s, 4H), 4.28 (m, 
8H), 3.98 (m, 4H), 3.77 (m, 4H), 3.62 (m, 8H), 3.40 (m, 4H); 13C NMR (125 MHz, 
CD2Cl2): δ = 154.8, 154.7, 135.0, 127.1, 125.6, 116.7, 116.6, 116.5, 114.8, 114.7, 110.7, 
106.1, 106.1, 71.3, 70.9, 70.7, 70.4, 70.2, 69.9, 69.89, 68.6, 68.4, 51.3, 51.2;[S5] HRMS 
(FAB): m/z calcd for C30H36N6O7S4: 720.1528; found: 720.1550. 
 S7
Scheme S4. Synthesis of the bistable [2]rotaxane 1·4PF6 
 
 
 
 
 
 
 
 
 
 
 
 
1·4PF6: The TTF/DNP-containing diazide 5 (9.7 mg, 0.013 mmol), CBPQT·4PF6 (15.5 
mg, 0.014 mmol), and the alkyne-functionalized stopper4 7 (14.9 mg, 0.028 mmol) were 
dissolved in DMF (0.18 mL) at room temperature to afford a deep green solution. Stock 
solutions of CuSO4·5H2O in DMF (20 μL, 0.006M) and ascorbic acid in DMF (20 μL, 
0.012M) were added. The solution was stirred at room temperature for 48 h. The crude 
product, obtained after the removal of the solvent, was purified by column 
chromatography (SiO2: Me2CO followed by a 1% w/v NH4PF6 solution in Me2CO). The 
green compound present in this salt solution was concentrated into a small volume and 
the pure product was precipitated from this concentrate following the addition of an 
excess of cold water. The bistable [2]rotaxane 1·4PF6 was isolated as a green solid (23 
mg, 60% yield, mp 150 ºC with decomposition); 1H NMR (600 MHz, CD3CN): δ = 
 S8
8.86−8.79 (m 12H), 8.66 (s, 2H), 8.63 (s, 2H), 7.93 (s, 1H), 7.69 (s, 3H), 7.78 (br, 2H), 
7.69−7.46 (m, 30H), 7.38−7.33 (m, 5H), 7.25 (br, 12H), 7.12 (br, 45H), 6.97−6.92 (m, 
3H), 6.85−6.77 (m, 8H), 6.76 (d, J = 7.6 Hz, 1H), 6.68 (d, J = 7.6 Hz, 1H), 6.42 (d, J = 
7.2 Hz, 2H), 6.14 (s, 1H), 6.03 (s, 2H), 5.87 (s, 1H), 5.66−5.58 (m, 6H), 5.49−5.38 (m, 
12H), 5.04 (s, 2H), 5.03 (s, 2H), 5.01 (s, 2H), 4.99 (s, 2H), 4.61−4.57 (m, 8H), 4.33 (br, 
4H), 4.25 (br, 4H), 4.11 (s, 2H), 4.09 (br 4H), 4.06 (br, 6H), 4.00−3.95 (m, 12H), 3.90 (br, 
6H), 3.84 (br, 4H), 3.79 (br, 6H), 3.74 (br, 2H), 3.71 (br, 2H), 3.61 (br, 2H), 2.83 (hextet, 
J = 6.9 Hz, 4H), 1.25 (br, H72), 1.18−1.16 (m, 24H); MS (ESI): m/z = 1294 [M – 2PF6]2+, 
814 [M – 3PF6]3+, 574 [M – 4PF6]4+; HRMS (FAB): m/z calcd for C144H156F12N10O9P2S4: 
1294.0130; found: 1294.0108 [M – 2PF6]2+. 
 
NMR Spectra of New Compounds 
Figure 1. 1H NMR spectrum of the diol derivative 4   
 
 
 
 
 
 
 
 
 δ 
 S9
Figure 2. 13C NMR spectrum of the diol derivative 4   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure 3. 1H NMR spectrum of the ditosyl derivative S1 
   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
δ 
δ 
 Figure 4. 13C NMR spectrum of the diol derivative S1 
   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
δ 
δ 
 S11
Figure 5. 1H NMR spectrum of the ditosyl derivative 5 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure 6. 13 C NMR spectrum of the ditosyl derivative 5 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
δ 
δ 
 S12
Figure 7. 1H NMR spectrum of the rotaxane 1·4PF6 
 
 
 
 
 
 
 
 
 
 
 
Figure 8. COSY spectrum of the rotaxane 1·4PF6 
 
 
 
 
 
 
 
 
 
 
 
δ 
    δ 
 S13
Figure 9. NOESY spectrum of the rotaxane 1·4PF6 
 
 
                                                             
 
(S1) Asakawa, M.; Dehaen, W.; L'abbé, G.; Menzer, S.; Nouwen, J.; Raymo, F. M.; 
Stoddart, J. F.; Williams, D. J. J. Org. Chem. 1996, 61, 9591–9595. 
(S2)   Yamamoto, T.; Tseng, H.-R.; Stoddart, J. F.; Balzani, V.; Credi, A.; Marchioni, F.; 
Venturi, M. Collect. Czech. Chem. Commun. 2003, 68, 1488–1514. 
(S3)   Tseng, H.-R.; Vignon, S. A.; Celestre, P. C.; Perkins, J.; Jeppesen, J. O.; Di Fabio, 
A.; Ballardini, R.; Gandolfi, M. T.; Venturi, M.; Balzani, V.;  Stoddart, J. F. Chem. 
Eur. J. 2004, 10, 155–172  
(S4)  Dichtel, W. R.; Miljanić, O. Š.; Spruell, J. M.; Heath, J. R.; Stoddart, J. F. J. Am. 
Chem. Soc. 2006, 128, 10388–10390. 
(S5) Some of the signals in the 13C NMR spectrum are duplicated because of the     
cis/trans isomerism.    
    δ 


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A Clicked Bistable [2]Rotaxane

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