Oscillating Emission of [2]Rotaxane Driven by Chemical Fuel

Oscillating Emission of [2]Rotaxane Driven by Chemical Fuel Amit Ghosh, a Indrajit Paul, a Matthias Adlung, b Claudia Wickleder, b Michael Schmittel*,a a Center of Micro- and Nanochemistry and Engineering, Organische Chemie I, Adolf Reichwein Str. 2, D-57068 Siegen, Germany. a Center of Micro- and Nanochemistry and Engineering, Anorganische Chemie II, Adolf Reichwein Str. 2, D-57068 Siegen, Germany.Email: schmittel@chemie.uni-siegen.de Table of Contents 1. Synthesis 1.1 General information S02 1.2 Synthesis overview S03 1.3 Synthesis of precursors S04 1.4 Synthesis of rotaxanes S08 2. NMR spectra S11 3. Comparison of NMR spectra S25 4. NMR studies in presence of chemical fuel S26 5. Variable temperature studies and determination of kinetic parameters S28 6. UV-vis spectra S29 7. ESI-MS spectra S32 8. Fluorescence spectra S37 9. Fluorescence studies in presence of chemical fuel S38 10. Temperature dependency of fluorescence S38 11. References S39 S1

1. Synthesis 1.1 General information. All reagents were obtained from commercial suppliers and used without further purifications. Technical grade solvents were distilled prior to use. Tetrahydrofuran (THF) was pre-dried over basic alumina and then distilled over potassium. Dimethylformamide (DMF) and triethylamine (Et 3 N) were distilled from calcium hydride. Diethyl ether (Et 2 O) was pre-dried over calcium hydride and then distilled from sodium. The melting points of compounds were measured on a Büchi SMP-11 instrument. 1 H-, 13 C-, and 1 H- 1 H-COSY NMR spectra were recorded at 298 K using the deuterated solvent as the lock. The chemical shifts refer to the residual protiated fraction of the solvent (CHCl 3 : δ H = 7.26, δ C = 77.0 ; CHDCl 2 : δ H = 5.32, δ C = 53.8 ; CHD 2 CN: δ H = 1.94, δ C = 1.32, 118.3 ). Abbreviations were used in 1 H NMR assignments to describe splitting patterns (s: singlet, d: doublet, t: triplet, dd: doublet of doublets, ddd: doublet of doublets of doublets, brs: broad singlet, td: triplet of doublets, quint: quintet, m: multiplet), the value of coupling constant(s) is reported in Hertz (Hz) and the number of protons are implied. The numbering of carbon atoms is usually not in accordance with IUPAC nomenclature guidelines. UV-vis spectra were measured on a Cary Win 50. Electrospray ionization mass spectra (ESI-MS) were recorded on a Thermo-Quest LCQ Deca instrument. Infrared spectra were recorded using a Perkin Elmer Spectrum-Two FT-IR spectrometer. Column chromatography was performed on silica gel 60 (60 230 mesh) or on neutral alumina (0.05 0.15 mm, Brockmann Activity 1). Thin Layer Chromatography (TLC) was performed using Merck silica gel (60 F254) or on neutral Al 2 O 3 (150 F254) sheets. Compounds 12, 1 13, 2 14, 3 15 4 and 16 5 were synthesized according to known protocols and in some cases modified procedures. The spectral data of these compounds were in good agreement with those in the literature reports. S2

1.2. Synthesis overview a) Synthesis of acid 1 Scheme S1: Synthesis of acid 1. Reagents and conditions: a) Ethyl cyanoacetate, K 2 CO 3, CuI, DMSO, 120 C, 12 h, 60%. b) CH 3 I, NaH, DMF, 0 C rt, 2 h, 60%. c) KOH, H 2 O - EtOH, rt, 2 h, 75%. b) Synthesis of stopper 8 Scheme S2: Synthesis of stopper 8. Reagents and conditions: a) NaBH 4, THF, rt, 2 h, 96%. b) PBr 3, toluene, 0 C, 1 h, 92%. c) NaN 3, DMF, 70 C, 2 h, 93%. c) Synthesis of precursor 6 Scheme S3: Synthesis of alkyne-ammonium axle 6. Reagents and conditions: a) 4-Bromobenzaldehyde, ammonium formate, methanol, 60 C, 16 h, 33%. b) Boc 2 O, Et 3 N, rt, 16 h, 62%. c) Trimethylsilylacetylene, DMF-Et 3 N, 85 C, 72 h, 80%. d) K 2 CO 3, methanol, rt, 1 h, 89%. e) TFA, NH 4 PF 6, methanol, rt, 28 h, 77%. S3

d) Synthesis of rotaxane R-2 Scheme S4: Synthesis of rotaxane R-2. Reagents and conditions: a) DB24C8 (9), CH 2 Cl 2, rt, 12 h, 60%. b) Azide 8, [Cu(MeCN) 4 ]PF 6, CH 2 Cl 2, rt, 16 h, 14%. c) MeI, NH 4 PF 6, CH 2 Cl 2, rt, 6 d, 26%. d) DBU, CD 2 Cl 2, rt, immediate, 100%. 1.3 Synthesis of precursors Compound 1 The oily compound 13 2 (250 mg, 1.23 mmol) was dissolved in 10 ml of EtOH and 10 ml of 10% aqueous KOH solution was added. The resulting mixture was stirred at room temperature for 2 h. Et 2 O was added and the aqueous layer was separated. The aqueous layer was washed twice with Et 2 O and acidified with 2 N H 2 SO 4. Triple extraction with Et 2 O and evaporation of the solvent afforded cyanoacetic acid 1 (150 mg, 856 µmol, 70%) in pure form. Mp: 95 C. IR (KBr): S4

3073, 3012, 2996, 2986, 2886, 2838, 2726, 2678, 2607, 2554, 1689, 1603, 1585, 1464, 1426, 1327, 1294, 1187, 1180, 1129, 1118, 1112, 1107, 1102, 1074, 1028, 1001, 949, 936, 812, 805, 708, 685, 667, 664 cm 1. 1 H NMR (CD 2 Cl 2, 400 MHz): δ 7.59-7.54 (m, 2H, 3-H), 7.47-7.39 (m, 3H, 1,2-H), 1.98 (s, 3H, 4-H). 13 C NMR (CD 2 Cl 2, 100 MHz): δ 170.0, 135.7, 129.6, 129.4, 126.3, 119.6, 48.4, 24.7. Anal.: Calcd for C 10 H 9 NO 2 1/10CH 2 Cl 2 : C, 66.04; H, 5.05; N, 7.63. Found, C, 66.46; H, 4.91; N, 7.62. Compound 17 Br 1 2 3 N H 17 Br 4-Bromobenzaldehyde (5.00 g, 27.3 mmol) was blended with 16 5 (6.91 g, 27.3 mmol) and ammonium formate (1.71 g, 27.3 mmol) into a reaction tube, to which methanol (10 ml) was added. The mixture was stirred at 60 C for 16 h under inert atmosphere. After completion of the reaction (monitored by TLC), the solvents were removed under reduced pressure. The crude product was extracted in DCM (20 ml) and washed successively with deionized water (50 ml 3) and saturated brine solution (30 ml 2). The organic layer was removed and the aqueous layer was re-extracted with DCM (20 ml). The combined organic layers were dried over anhydrous MgSO 4 and evaporated in vacuo. The column chromatographic purification (R f = 0.5, EtOAc : hexane = 1:10) of crude product on silica gel using 10% EtOAc in hexane provided compound 17 as white solid (3.20 g, 9.01 mmol, 33%). Mp: 41 C. IR (KBr): 2924, 2865, 2796, 1638, 1587, 1485, 1453, 1406, 1369, 1330, 1277, 1194, 1128, 1068, 1009, 927, 807, 752, 689, 649, 620 cm 1. 1 H NMR (CDCl 3, 400 MHz): δ 7.45 (d, 3 J = 8.0 Hz, 4H, 2-H), 7.21 (d, 3 J = 8.0 Hz, 4H, 1-H), 3.74 (s, 4H, 3-H). 13 C NMR (CDCl 3, 100 MHz): δ 139.1, 131.5, 129.8, 120.8, 52.3. ESI-MS: Calcd for C 14 H 13 Br 2 N m/z = 355.9. Found [17 H] + m/z = 356.0. Anal.: Calcd for C 14 H 13 Br 2 N: C, 47.36; H, 3.69; N, 3.94. Found, C, 47.73; H, 3.81; N, 3.84. S5

Compound 18 6 Di-tert.-butyl dicarbonate (730 mg, 3.35 mmol) and Et 3 N (564 mg, 5.58 mmol) were added to a solution of 17 (990 mg, 2.79 mmol) in dichloromethane (20 ml). Then the mixture was stirred at room temperature for 16 h. The solvent was evaporated under reduced pressure. The crude product was purified by column chromatography (R f = 0.5, dichloromethane : hexane = 1:1) using 50% dichloromethane in hexane to yield the Boc-protected dibromide 18 as colorless liquid (800 mg, 1.76 mmol, 62%). IR (KBr): 2977, 2929, 1694, 1592, 1488, 1456, 1423, 1400, 1366, 1243, 1163, 1120, 1072, 1012, 973, 931, 882, 840, 799, 767,724 cm 1. 1 H NMR (CDCl 3, 400 MHz): δ 7.44 (d, 3 J = 8.4 Hz, 4H, 2-H), 7.04 (brs, 4H, 1-H), 4.35 (s, 2H, 3/3 -H), 4.27 (s, 2H, 3 /3-H), 1.48 (s, 9H, m-h). 13 C NMR (CDCl 3, 100 MHz): δ 155.6, 136.7, 131.5, 129.5, 128.9, 121.0, 80.3, 48.8, 48.6, 28.2. Anal.: Calcd. for C 86 H 63 N 7 Zn: C, 50.13; H, 4.65; N, 3.08. Found, C, 50.22; H, 4.62; N, 3.39. Compound 19 6 Copper iodide (29.0 mg, 150 µmol), trimethylsilylacetylene (1.51 g, 15.3 mmol) and compound 18 (1.40 g, 3.08 mmol) were added to a degassed mixture of Et 3 N (15 ml) and DMF (15 ml). Then, tetrakis(triphenylphosphine)palladium(0) (177 mg, 150 µmol) was added and the mixture heated at 85 C for 72 h. After cooling to room temperature the solvent was evaporated under reduced pressure. The residue was dissolved in DCM (25 ml) and subsequently washed with water (30 ml 2). The organic layer was dried over anhydrous MgSO 4 and evaporated in vacuo. The residue was purified by column chromatography (R f = 0.4, dichloromethane : hexane = 1:1) on silica gel using 50% dichloromethane in hexane to yield compound 5 as a yellow liquid (1.20 S6

g, 2.45 mmol, 80%). K 2 CO 3 (1.05 g, 7.65 mmol) was added to a solution of 5 (750 mg, 1.53 mmol) in MeOH (10 ml) and THF (15 ml). The mixture was stirred at room temperature for 1 h (TLC) and partitioned between dichloromethane and water. The water phase was washed with dichloromethane, thereafter the organic layer was dried over anhydrous MgSO 4 and evaporated in vacuo. The colorless liquid 19 (470 mg, 1.36 mmol, 89%) was used for the next reaction without further purification. IR (KBr): 3293, 3032, 2977, 2930, 2109, 1694, 1609, 1506, 1456, 1405, 1367, 1306, 1246, 1163, 1122, 1020, 974, 938, 884, 850, 821, 769, 658, 529, 516 cm 1. 1 H NMR (CDCl 3, 400 MHz): δ 7.45 (d, 3 J = 8.0 Hz, 4H, 2-H), 7.18 (brs, 4H, 1-H), 4.41 (s, 2H, 3/3 - H), 4.31 (s, 2H, 3 /3-H), 3.07 (s, 2H, 4-H), 1.47 (s, 9H, m-h). 13 C NMR (CDCl 3, 100 MHz): δ 155.8, 138.7, 132.3, 127.8, 127.2, 121.0, 83.4, 80.5, 49.4, 49.1, 28.4. Anal.: Calcd. for C 23 H 23 NO 2 : C, 79.97; H, 6.71; N, 4.05; Zn, 4.18. Found: C, 79.62; H, 6.76; N, 4.39. Compound 6 6 Compound 19 (400 mg, 1.16 mmol) was dissolved in a mixture of MeOH (10 ml) and TFA (10 ml) and stirred at room temperature for 24 h. After adding saturated aqueous NH 4 PF 6 solution (10 ml) the mixture was further stirred for 4 h. Then the organic solvent was evaporated. The precipitate was filtered off and washed with water several times to afford 6 (350 mg, 894 μmol, 77%) as brown solid. Mp: Decomposition > 145 C. IR (KBr): 3300, 3034, 2834, 2352, 1666, 1509, 1458, 1202, 1167, 1139, 990, 825, 797, 743, 722, 667 cm 1. 1 H NMR (CD 3 CN, 400 MHz): δ 7.52 (d, 3 J = 8.4 Hz, 4H, 2-H), 7.45 (d, 3 J = 8.4 Hz, 4H, 1-H), 4.18 (s, 4H, 3-H), 3.45 (s, 2H, 4- H). 13 C NMR (CD 3 CN, 100 MHz, 298 K): δ 133.3, 133.1, 131.3, 123.9, 83.5, 80.2, 51.3. ESI-MS: Calcd. for [C 18 H 16 N] + m/z = 246.1. Found [6 H] + m/z = 246.0. S7

Compound 8 Compound 15 (1.85 g, 6.82 mmol) was dissolved in 20 ml of dry DMF. After addition of sodium azide (665 mg, 10.2 mmol) the reaction mixture was stirred under argon for 2 h maintaining the temperature at 70 C. After completion of the reaction (monitored by TLC), the reaction mixture was diluted with dichloromethane and the organic layer was separated and washed repeatedly with ice cold water. The organic phase was dried over anhydrous Na 2 SO 4 and the solvent was evaporated in vacuo. The residue was purified by column chromatography (R f = 0.4, EtOAc : hexane = 1:20) on silica gel using 5% EtOAc in hexane to yield compound 8 as a yellow powder (1.49 g, 6.38 mmol, 93%). Mp: 58 C. IR (KBr): 2922, 2096, 2056, 1622, 1445, 1376, 1334, 1280, 1228, 1177, 1156, 1084, 1045, 958, 896, 871, 858, 795, 738, 603 cm 1. 1 H NMR (CD 2 Cl 2, 400 MHz): δ 8.55 (s, 1H, 1-H), 8.32 (d, 3 J = 8.8 Hz, 2H, 5-H), 8.09 (d, 3 J = 8.4 Hz, 2H, 2-H), 7.62-7.58 (m, 2H, 4-H), 7.54-7.49 (m, 2H, 3-H), 5.36 (s, 2H, 6-H). 13 C NMR (CDCl 3, 100 MHz): δ 131.3, 130.7, 129.3, 128.9, 126.8, 125.2, 125.2, 123.5, 46.3. Anal.: Calcd for C 15 H 11 N 3 : C, 77.23; H, 4.75; N, 18.01. Found: C, 77.29; H, 4.74; N, 17.92. 1.4 Synthesis of rotaxanes Synthesis of R-3 15 14 13 12 N N N 11 10 1 2 O O PF O 6 4 3 O N 7 H H O O 6 O O 5 8 9 R-3 N N N S8

A solution of 6 (200 mg, 511 µmol) and 9 (= DB24C8: 688 mg, 1.53 mmol) in CH 2 Cl 2 (35 ml) was stirred at room temperature for 12 h. Then, a solution of azide 8 (358 mg, 1.53 mmol) and [Cu(CH 3 CN) 4 ]PF 6 (190 mg, 510 µmol) in CH 2 Cl 2 (15 ml) were added to the reaction mixture that was stirred overnight at room temperature. The resulting mixture was diluted with CH 2 Cl 2 (40 ml) and washed with EDTA (aq) and H 2 O (50 ml). The organic layer was dried over anhydrous Na 2 SO 4. The solvent was removed under reduced pressure and the resulting residue was purified by column chromatography (R f = 0.4, MeOH : CH 2 Cl 2 = 1 : 100) over neutral Al 2 O 3 to yield R-3 (95.0 mg, 72.8 µmol 14%) as a brown powder (after adding n-hexane to the concentrated fractions). Mp: 161 C. IR (KBr): 2926, 2875, 1732, 1660, 1625, 1598, 1504, 1452, 1384, 1356, 1323, 1317, 1252, 1208, 1123, 1049, 953, 841, 799, 745, 702, 601 cm 1. 1 H NMR (CD 2 Cl 2, 400 MHz): δ 8.64 (s, 2H, 1-H), 8.43 (dd, 3 J = 8.8 Hz, 4 J = 0.8 Hz, 4H, 11-H), 8.14-8.11 (m, 4H, 14-H), 7.65 (ddd, 3 J = 8.8 Hz, 4 J = 6.8 Hz, 5 J = 1.2 Hz, 4H, 13-H), 7.56 (ddd, 3 J = 8.4 Hz, 4 J = 6.4 Hz, 5 J = 0.8 Hz, 4H, 12-H), 7.47 (d, 3 J = 8.4 Hz, 4H, 3-H), 7.46 (s, 2H, 15-H), 7.21 (d, 3 J = 8.4 Hz, 4H, 2-H), 6.64 (dd, 3 J = 6.0 Hz, 4 J = 2.8 Hz, 4H, 8-H), 6.60 (s, 4H, 10-H), 6.56 (dd, 3 J = 6.0 Hz, 4 J = 2.8 Hz, 4H, 9-H), 4.54-4.49 (m, 4H, 4-H), 4.00-3.96 (m, 8H, 5-H), 3.67-3.63 (m, 8H, 6-H), 3.35 (s, 8H, 7-H). 13 C NMR (CD 2 Cl 2, 100 MHz): δ 147.7, 146.8, 132.0, 131.9, 131.5, 131.1, 130.2, 129.9, 129.8, 127.9, 125.8 (2C), 124.6, 123.5, 121.8, 120.2, 113.0, 71.0, 70.5, 68.4, 52.6, 46.8. ESI-MS: Calcd for [C 72 H 70 N 7 O 8 ] + m/z = 1160.5. Found [(R-3) PF 6 ] + m/z = 1161.1. Anal.: Calcd. for C 72 H 70 F 6 N 7 O 8 P 4/3C 6 H 14 : C, 67.61; H, 6.29; N, 6.90. Found: C, 67.24; H, 5.88; N, 6.50. Synthesis of R-1 A solution of R-3 (80.0 mg, 70.0 µmol) in iodomethane (10 ml) was stirred at room temperature for 6 days. The solvent was removed under reduced pressure and the residue was re-dissolved in S9

CH 2 Cl 2 /acetone/water 1:1:2 (20 ml). An excess of NH 4 PF 6 was added and the mixture was stirred for 3 hours. The phases were separated and the aqueous layer was extracted with CH 2 Cl 2. The combined organic solvents were washed with H 2 O, dried with Na 2 SO 4 and concentrated under reduced pressure and the resulting residue was purified by column chromatography (R f = 0.3, MeOH : CH 2 Cl 2 = 1 : 100) over neutral Al 2 O 3 to yield R-1 (30.0 mg, 18.4 µmol, 26%) as a white solid. Mp: 136 C. IR (KBr): 2924, 2852, 1730, 1626, 1594, 1506, 1454, 1280, 1253, 1208, 1126, 1103, 1056, 954, 843, 742, 627, 600 cm 1. 1 H NMR (CD 2 Cl 2, 400 MHz): δ 8.75 (s, 2H, 1-H), 8.41 (d, 3 J = 8.8 Hz, 4H, 11-H), 8.18 (d, 3 J = 8.4 Hz, 4H, 14-H), 8.03 (s, 2H, 15-H), 7.91 (brs, 2H, N-H), 7.78 (ddd, 3 J = 8.8 Hz, 4 J = 6.4 Hz, 5 J = 1.2 Hz, 4H, 13-H), 7.65-7.61 (ddd, 3 J = 8.0 Hz, 4 J = 6.0 Hz, 5 J = 0.8 Hz, 4H, 12-H), 7.48 (d, 3 J = 8.4 Hz, 4H, 3-H), 7.25 (d, 3 J = 8.4 Hz, 4H, 2-H), 6.83 (s, 4H, 10-H), 6.50 (dd, 3 J = 6.1 Hz, 4 J = 3.6 Hz, 4H, 8-H), 6.31 (dd, 3 J = 6.1 Hz, 4 J = 3.6 Hz, 4H, 9-H), 4.82-4.76 (m, 4H, 4-H), 4.09 (s, 6H, 16-H), 3.95-3.91 (m, 8H, 5-H), 3.78-3.74 (m, 8H, 6-H), 3.60 (s, 8H, 7-H). 13 C NMR (CD 2 Cl 2, 100 MHz): δ 147.3, 143.0, 135.9, 131.8, 131.7, 131.6, 130.5, 130.0, 129.8, 129.0, 128.5, 126.1, 123.0, 122.6, 121.4, 120.5, 112.3, 71.0, 70.7, 67.7, 52.3, 50.6, 39.1. ESI-MS: Calcd for [C 74 H 76 F 12 N 7 O 8 P 2 ] + m/z = 1480.5. Found: [(R-1) PF 6 ] + m/z = 1480.8. Calcd for [C 74 H 75 F 6 N 7 O 8 P] + m/z = 1334.5. Found: [(R-1) H (PF 6 ) 2 ] + m/z = 1334.5. Anal. calcd for C 74 H 76 F 18 N 7 O 8 P 3 : C, 54.65; H, 4.71; N, 6.03. Found: C, 54.57; H, 4.78; N, 5.85. Synthesis of R-2 In an NMR tube, R-1 (1.24 mg, 76.0 µmol) and DBU (174 µg, 76.0 µmol) were dissolved in 500 µl of CD 2 Cl 2. Yield quantitative. 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 8.56 (s, 2H, 1-H), 8.43 (d, 3 J = 6.0 Hz, 4H, 11-H), 8.06 (d, 3 J = 6.0 Hz, 4H, 14-H), 7.59-7.42 (m,18h, 15-, 12-, 13-H, 3-H, 2-H), 6.85 (dd, 3 J = 6.0 Hz, 4 J = 3.6 Hz, 4H, 8-H), 6.79 (s, 4H, 10-H), 6.60 (dd, 3 J = 6.0 Hz, 4 J = S10

3.6 Hz, 4H, 9-H), 4.19 (s, 4H, 4-H), 3.60 (s, 1H, N-H), 3.26-3.24 (m, 24H, 6-, 5-, 7-H), 3.05 (s, 6H, 16-H). ESI-MS: [C 74 H 75 F 6 N 7 O 8 P] + m/z = 1334.5. Found [(R-2) PF 6 ] + m/z = 1334.5. 2. NMR spectra: 1 H, 13 C, 1 H 1 H COSY 4 3 1,2 CDHCl 2 Figure S1. 1 H NMR spectrum (CD 2 Cl 2, 400 MHz) of compound 1. CD 2 Cl 2 Figure S2. 13 C NMR spectrum (CD 2 Cl 2, 100 MHz) of compound 1. S11

2 1 CHCl 3 2 7.5 7.4 7.3 7.2 1 3 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Figure S3. 1 H NMR spectrum (CDCl 3, 400 MHz) of compound 17. CDCl 3 Figure S4. 13 C NMR spectrum (CDCl 3, 100 MHz) of compound 17. S12

2 CHCl 3 1 3 Figure S5. 1 H- 1 H COSY NMR spectrum (CDCl 3, 400 MHz) of compound 17. m 2 1 2 CHCl 3 1 3/3 3 /3 Figure S6. 1 H NMR spectrum (CDCl 3, 400 MHz) of compound 18. S13

CDCl 3 Figure S7. 13 C NMR spectrum (CDCl 3, 100 MHz) of compound 18. 2 CHCl 3 1 3/3 3 /3 m Figure S8. 1 H- 1 H COSY NMR spectrum (CDCl 3, 400 MHz) of compound 18. S14

2 2 1 m 7.5 7.4 7.3 7.2 7.1 4 CHCl 3 1 3/3 3 /3 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Figure S9. 1 H NMR spectrum (CDCl 3, 400 MHz) of compound 19. CDCl 3 Figure S10. 13 C NMR spectrum (CDCl 3, 100 MHz) of compound 19. S15

2 CHCl 3 4 m 1 3/ 3 3 /3 Figure S11. 1 H- 1 H COSY NMR spectrum (CDCl 3, 400 MHz) of compound 19. 2 1 3 4 H 2 O CD 2 HCN Figure S12. 1 H NMR spectrum (CD 3 CN, 400 MHz) of compound 6. S16

CD 3 CN Figure S13. 13 C NMR spectrum (CD 3 CN, 100 MHz) of compound 6. 2 1 3 4 H 2 O CD 2 HCN Figure S14. 1 H- 1 H COSY NMR spectrum (CD 3 CN, 400 MHz) of compound 6. S17

6 1 5 2 4 3 CHCl 3 Figure S15. 1 H NMR spectrum (CDCl 3, 400 MHz) of compound 8. CDCl 3 Figure S16. 13 C NMR spectrum (CDCl 3, 100 MHz) of compound 8. S18

6 1 5 2 4 3 CHCl 3 Figure S17. 1 H- 1 H COSY NMR spectrum (CDCl 3, 400 MHz) of compound 8. S19

15 10 1 11 14 13 12 3 2 8 9 7 15 10 CDHCl 2 1 11 14 3 13 12 2 8 9 4 5 6 H 2 O Figure S18. 1 H NMR spectrum (CD 2 Cl 2, 400 MHz) of compound R-3. CD 2 Cl 2 Figure S19. 13 C NMR spectrum (CD 2 Cl 2, 100 MHz) of compound R-3. S20

15 10 7 11 14 1 13 12 3 2 8 9 CDHCl 2 4 5 6 Figure S20. 1 H- 1 H COSY NMR spectrum (CD 2 Cl 2, 400 MHz) of compound R-3. S21

10 1 11 14 15 13 12 3 2 8 9 N-H 16 7 1 11 14 3 15 13 12 2 10 8 9 CDHCl 2 4 5 6 H 2 O Figure S21. 1 H NMR spectrum (CD 2 Cl 2, 400 MHz) of compound R-1. CD 2 Cl 2 Figure S22. 13 C NMR spectrum (CD 2 Cl 2, 100 MHz) of compound R-1. S22

CDHCl 2 16 7 1 11 14 15 3 2 13 12 N-H 10 8 9 4 5 6 Figure S23. 1 H- 1 H COSY NMR spectrum (CD 2 Cl 2, 400 MHz) of compound R-1. S23

1 11 14 15, 12, 13, 3, 2 10 CDHCl 2 7, 5, 6 DBU-H + DBU-H + DBU-H + DBU-H + 1 11 14 15, 12, 13, 3, 2 8 9 4 DBU-H + N-H 16 H 2 O DBU-H + Figure S24. 1 H NMR spectrum (CD 2 Cl 2, 400 MHz) of compound R-2. S24

3. Comparison of NMR spectra of R-1 and R-2. 10 R-2 8 9 4 NH 16 11 1 12 CDHCl 2 16 R-1 10 1 11 12 NH 2 8 9 4 Figure S25. Partial 1 H NMR spectra (400 MHz, CD 2 Cl 2, 298 K) of R-1 and R-2. S25

4. NMR studies in presence of chemical fuel 1a 1 CDHCl 2 4 1a 1 4a Figure S26. 1 H NMR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction mixture of R-2 and the chemical fuel 1 (after 45 s) showing R-1 and R-2 in a 2:3 ratio. S26

a) 1a, 2a, 3a 4a 5a b) 10 CDHCl 2 15, 12, 13, 3, 2 4 5, 6, 7 1 11 14 8 9 N-H 16 Figure S27. 1 H NMR spectra (400 MHz, CD 2 Cl 2, 298 K) of the reaction mixture of R-2 and the chemical fuel 1 (after 9 min) showing R-2 and 4 in a 1:1 ratio: a) Characterization of the signals arising from compound 4, b) characterization of all the signals for R-2 (the unmarked signals are for DBU-H + ). S27

5. Variable temperature studies and determination of kinetic parameters for R-2 1 UC 1 C 1.00 1.13 1 C 1 UC -75 C -65 C -50 C -45 C -40 C -35 C -30 C -27 C -25 C 0 C 25 C Figure S28. Partial 1 H VT-NMR (CD 2 Cl 2, 600 MHz) of R-2 showing the aromatic region and the splitting of proton 1-H (red asterisk marked). S28

a) Experimental Simulated b) -75 C -65 C k = 15 s -1 k = 45 s -1 y = -3.765x + 16.516 R² = 0.996-50 C k = 160 s -1-45 C k = 370 s -1 25 C k = 15000 s -1 9.1 8.9 8.7 8.5 9.1 8.9 8.7 8.5 () () Figure S29. (a) Partial 1 H VT-NMR (CD 2 Cl 2, 600 MHz) of R-2 (aromatic region) shows the splitting of 1-H (red asterisk marked) and (b) Eyring plot for translational dynamics in R-2. 6. UV-vis spectra 0.8 257 nm 0.7 0.6 Absorption 0.5 0.4 0.3 0.2 0.1 354 nm 372 nm 392 nm 0.0 200 250 300 350 400 Wavelength (nm) Figure S30. UV-vis spectrum of rotaxane R-1 (3.69 10 6 M) in CH 2 Cl 2 at 298 K. S29

0.8 257 nm 0.7 0.6 Absorption 0.5 0.4 0.3 0.2 0.1 353 nm 371 nm 391 nm 0.0 200 250 300 350 400 Wavelength (nm) Figure S31. UV-vis spectrum of rotaxane R-1 (3.69 10 6 M) in CH 2 Cl 2 at 298 K after addition of 1.5 equiv of DBU. S30

0.8 0.7 0.6 0.5 371 nm 372 nm R-1 + 1.0 equiv of DBU R-1 + 0.8 equiv of DBU R-1 + 0.6 equiv of DBU R-1 + 0.4 equiv of DBU R-1 + 0.2 equiv of DBU R-1 Absorption 0.4 0.3 0.2 0.1 0.0 330 340 350 360 370 380 390 400 410 Wavelength (nm) Figure S32. UV-vis titration of complex R-1 (4.3 10 5 M) vs. DBU (1.075 10 3 M) in CH 2 Cl 2 at 298 K. S31

7. ESI-MS spectra 100 356.0 [17+H] + 356.1 90 80 358.1 70 354.1 Relative Abundance 60 50 40 355.1 357.1 359.0 30 20 10 0 200 400 600 800 1000 1200 1400 1600 1800 2000 m/z Figure S33. ESI-MS spectrum of compound 17 in CH 2 Cl 2. S32

100 279.2 [6(CH 3 OH)+H] + 246.2 90 80 246.0[6+H] + 70 Relative Abundance 60 50 40 247.2 248.2 30 20 10 0 200 400 600 800 1000 1200 1400 1600 1800 2000 m/z Figure S34. ESI-MS spectrum of compound 6 in CH 2 Cl 2. S33

100 1161.3[(R-3) PF 6 ] + 90 1161.8 1162.5 80 70 Relative Abundance 60 50 40 1163.3 1164.3 30 20 10 0 200 400 600 800 1000 1200 1400 1600 1800 2000 m/z Figure S35. ESI-MS spectrum of compound R-3 in CH 2 Cl 2. S34

100 1335.2 1480.8 [(R-1) PF 6 ] + 90 1336.1 80 70 Relative Abundance 60 50 40 1337.0 1338.1 30 1334.5 [(R-1) H (PF 6 ) 2 ] + 20 10 0 200 400 600 800 1000 1200 1400 1600 1800 2000 m/z Figure S36. ESI-MS spectrum of compound R-1 in CH 2 Cl 2. S35

100 1334.2 1334.3[(R-2)PF 6 ] + 90 80 1335.2 70 Relative Abundance 60 50 40 1336.1 1337.1 30 20 153.3 10 0 200 400 600 800 1000 1200 1400 1600 1800 2000 m/z Figure S37. ESI-MS spectrum of compound R-2 in CH 2 Cl 2. S36

8. Fluorescence spectra Fluorescence measurements were performed in quartz cells with CH 2 Cl 2 as solvent. 70 Fluorescence intensity / au 60 50 40 30 20 10 0 380 400 420 440 460 480 500 520 540 Wavelength / nm Figure S38. Fluorescence spectrum of rotaxane R-1 (1 x 10 5 M) at 298 K (λ exc = 252 nm). 700 Fluorescence intensity / au 600 500 400 300 200 100 0 380 400 420 440 460 480 500 520 540 Wavelength / nm Figure S39. Fluorescence spectrum of rotaxane R-2 (1 x 10 5 M) at 298 K (λ exc = 252 nm). S37

9. Fluorescence studies in presence of chemical fuel 600 550 500 F.I 421 / au 450 400 350 300 250 200 0 3 6 9 12 15 18 21 24 27 Time / min Figure S40. Fluorescence intensity of R-2 (c = 10 5 M, in CH 2 Cl 2 at 25 C) at 421 nm vs. time after addition of 1. 10. Temperature dependency of fluorescence fluorescence intensity / au 800 700 600 500 400 300 200 100 75 C 55 C 35 C 20 C 5 C 25 C 0 375 400 425 450 475 500 525 550 wavelength / nm Figure S41. Variable temperature fluorescence spectra of R-1 (λ exc = 252 nm, 1 10 5 M) in CH 2 Cl 2. S38

fluorescence intensity / au 5000 4500 4000 3500 3000 2500 2000 1500 1000 75 C 55 C 35 C 20 C 5 C 25 C 500 0 350 375 400 425 450 475 500 525 550 wavelength / nm Figure S42. Variable temperature fluorescence spectra of R-2 (λ exc = 252 nm, 1 10 5 M) in CH 2 Cl 2. 11. References 1. Hu, C; Hong, G; Qian, X; Kim, K. R; Zhu, X; Wang, L. Org. Biomol. Chem. 2017, 15, 4984. 2. Mallia, C. J; Englert, L; Walter, G. C; Baxendale, I. R. Beilstein J. Org. Chem. 2015, 11, 875 3. Rodriguez, K. J; Hanlon, A. M; Lyon, C. K; Cole, J. P; Tuten, B. T; Tooley, C. A; Berda, E. B; Pazicni, S. Inorg. Chem. 2016, 55, 9493. 4. Liu, H. W; Xu, S; Wang, P; Hu, X. X; Zhang, J; Yuan, L; Zhang, X. B; Tan, W. Chem. Commun. 2016, 52, 12330. 5. Sumino, S; Uno, M; Fukuyama, T; Ryu, I; Matsuura, M; Yamamoto, A; Kishikawa, Y. J. Org. Chem. 2017, 82, 5469. 6. Hsu, C. C; Lai, C. C; Chiu, S. H. Tetrahedron 2009, 65, 2824. S39