Controlling the Recognition and Reactivity of Alkyl Ammonium. Guests Using an Anion Coordination-Based Tetrahedral Cage

Transcription

1 Supporting Information Controlling the Recognition and Reactivity of Alkyl Ammonium Guests Using an Anion Coordination-Based Tetrahedral Cage Wenyao Zhang,, Dong Yang,, Jie Zhao, Lekai Hou, Jonathan L. Sessler, Xiao-Juan Yang, Biao Wu * Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi an , China, wubiao@nwu.edu.cn Center for Supramolecular Chemistry and Catalysis, Shanghai University, Shanghai , China Table of Contents: S1. General considerations... S2 S2. Synthesis of ligand L... S3 S3. Synthesis of cationic guests... S6 S4. Synthesis of the self-assembled complexes... S9 S5. Crystal structures of the guest-inclusion complexes... S13 S6. 1 H and 2D NMR spectroscopy... S16 S7. Isothermal titration calorimetry studies... S41 S8. Analysis of guest exchange... S43 S9. High-resolution MS studies... S43 S10. Studies of DABCO methylation... S50 S11. X-ray crystallography... S52 S12. Volume calculations... S57 S13. Supporting references... S S1

2 S1. General considerations o-nitro-phenylisocyanate and p-nitro-phenylisocyanate were purchased from Alfa Aesar and used as received. All solvents and other reagents were of reagent grade quality and purchased commercially. 1 H NMR, 13 C NMR, 1 H- 1 H COSY, 1 H- 1 H NOESY and 31 P NMR spectra were recorded on a Bruker Avance III-400 MHz NMR spectrometer at 400, 100, and 162 MHz, respectively, using residual solvent peaks as the internal standard for the 1 H and 13 C spectral analyses, and triphenylphosphine as the internal standard for the 31 P NMR spectroscopic analyses. Infrared (IR) spectra were recorded on a Bruker EQUIOX-55 spectrometer. Isothermal titration calorimetry (ITC) measurements were carried out using a VP-ITC (Malvern) at 298 K. Computer fitting of the data was performed using the VP-ITC software. The mass spectra of ligand L, intermediates, and 3 guests were measured with a Bruker microtof-q II ESI-Q-TOF LC/MS/MS spectrometer. The samples were dissolved in acetonitrile and measured using the following ESI parameters: Spray voltage = 4.5 kv; dry gas at 8.0 l/min; temperature: 150 C; collision energy: 2 ev; mass range: amu. Scheme 1. Synthesis of ligand L. S2

3 S2. Synthesis of ligand L 2,4,6-Tris(4-bromophenyl)-1,3,5-triazine (b) Compound b was prepared according to reported literature procedures. 1 1 H NMR (400 MHz, CDCl 3, ppm): δ 8.62 (d, J = 8.00 Hz, 2H, H1), 7.72 (d, J = 8.00 Hz, 2H, H2). Figure S1. 1 H NMR spectrum of compound b (400 MHz, CDCl 3, 296 K). 2,4,6-Tris(4-aminophenyl)-1,3,5-triazine (c) Compound c was prepared according to reported literature procedures. 2 1 H NMR (400 MHz, DMSO-d 6, ppm): δ 8.36 (d, J = 8.00 Hz, 2H, H1), 6.70 (d, J = 8.00 Hz, 2H, H2), 5.91 (s, 2H, Ha). Figure S2. 1 H NMR spectrum of compound c (400 MHz, DMSO-d 6, 296 K). Compound d A THF (15 ml) solution of c (0.45 g, 1.27 mmol) was added to a THF (15 ml) solution of o-nitro-phenylisocyanate (1.04 g, 6.31 mmol). After stirring overnight,the resulting precipitate was filtered off and washed several times with diethyl ether. It was then dried under vacuum to yield analytically pure d as a yellow solid (0.62 g, 0.73 mmol, 57.5%). 1 H NMR (400 MHz, DMSO-d 6, ppm): δ (s, 1H, Hb), 9.71 (s, 1H, Ha), 8.67 (d, J = 8.0 Hz, 2H, H1), 8.33 (d, J = 8.0 Hz,1H, H6), 8.11 (d, J = 8.0 Hz, 1H, H3), 7.75 (t, 3H, H2/4), 7.25 (d, J = 8.0 Hz, 1H, H5). 13 C NMR (100 MHz, DMSO-d 6, ppm): δ (CO), (CO), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (CH). IR (KBr, ν/cm 1 ): 3318, 1610 (CO), 1488, 1338, 1179, 1135, 804, 749,519. ESI-MS: m/z , [M+K] +. S3

4 Figure S3. 1 H NMR spectrum of compound d (400 MHz, DMSO-d 6, 296 K). Figure S4. 13 C NMR spectrum of compound d (100 MHz, DMSO-d 6, 296 K). Compound e Hydrazine monohydrate (2.0 ml) was added dropwise to a suspension of d (0.2 g, 0.24 mmol) and Pd/C 10% (0.02 g, cat.) in ethanol (20 ml). After heating at reflux with stirring overnight, the solid was filtered off via suction filtration and then redissolved in DMF (10 ml) and filtered through Celite to remove the Pd/C. The resulting DMF solution was poured into water (100 ml) to induce precipitation. The precipitate was collected and washed several times with ethanol and diethyl ether, then dried under vacuum to give e as a white solid (0.14 g, mmol, 78%). 1 H NMR (400 MHz, DMSO-d 6, ppm): δ 9.28 (s, 1H, Hb), 8.67 (d, J = 8.0 Hz, 2H, H1), 7.84 (s, 1H, Ha), 7.73 (d, J = 8.0 Hz, 2H, H2), 7.38 (d, J = 4.0 Hz, 1H, H3), 6.88 (d, J = 8.0 Hz, 1H, H4), 6.77 (d, J = 8.0 Hz, 1H, H6), 6.60 (s, 1H, H5), 4.86 (s, 2H, Hc). 13 C NMR (100 MHz, DMSO-d 6, ppm): δ (C), (CO), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (CH). IR (KBr, ν/cm 1 ): 3336, 1593(CO), 1469, 1364, 1302, 1179, 1012, 801, 748. ESI-MS: m/z , [M+K] +. Figure S5. 1 H NMR spectrum of compound e (400 MHz, DMSO-d 6, 296 K). S4

5 Figure S6. 13 C NMR spectrum of compound e (100 MHz, DMSO-d 6, 296 K). Ligand L Compound e (0.4 g, 0.53 mmol) was dissolved in 3 ml DMF and the resulting solution was added dropwise into a 15 ml THF solution of p-nitrophenylisocyanate (0.51 g, 3.17 mmol). The mixture was heated at reflux for 12 hours and the resulting precipitate filtered off and washed several times with diethyl ether, before being dried under vacuum to yield L as a brownish solid (0.54 g, 0.43 mmol, 81%). 1 H NMR (400 MHz, DMSO-d 6, ppm): δ 9.86 (s, 1H, Hd), 9.58 (s, 1H, Hc), 8.67 (d, J = 4.0 Hz, 2H, H1), 8.31 (s, 1H, Hb), 8.21 (d, 3H, H8/a), 7.74 (m, 4H, H2/7), 7.67 (d, 1H, H3), 7.62 (d, J = 1.2 Hz,1H, H6), 7.16 (s, J = 1.2 Hz, 4H, H4/5). 13 C NMR (100 MHz, DMSO-d 6, ppm): δ (C), (CO), (CO), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (CH), (CH), (CH), (CH), 117.7(CH), (CH). IR (KBr, ν/cm 1 ): 3353, 1672 (CO), 1496, 1320, 1161, 1118, 739. ESI-MS: m/z , [M+K] +. Figure S7. 1 H NMR spectrum of ligand L (400 MHz, DMSO-d 6, 296 K). Figure S8. 13 C NMR spectrum of compound L (100 MHz, DMSO-d 6, 296 K). S5

6 S3. Synthesis of cationic guests Cationic guests were prepared according to appropriate literature procedures. Literature citations and characterization data are provided for each guest below. Figure S9. The four types of cationic guests used in this study. Ethyl-trimethyl-ammonium bromide (N 1112 Br) 3 Figure S10. 1 H NMR spectrum of compound N 1112 Br (400 MHz, CD 3 CN, 296 K). S6

7 Propyl trimethylammonium bromide (N 1113 Br) 3 Figure S11. 1 H NMR spectrum of compound N 1113 Br (400 MHz, CD 3 CN, 296 K). N-Methyldiazabicyclooctane iodide (MeD I) 3 Figure S12. 1 H NMR spectrum of compound MeD I (400 MHz, CD 3 CN, 296 K). 5-Azoniaspiro[4.4]nonane bromide (ASN Br) 3 Figure S13. 1 H NMR spectrum of ASN Br (400 MHz, CD 3 CN, 296 K). 1,4-Dimethyl-1,4-diazabicyclo[2.2.2]octane iodie (MeDMe I 2 ) 4 Figure S14. 1 H NMR spectrum of MeDMe I 2 (400 MHz, CD 3 CN, 296 K). S7

8 Isobutyltrimethylammonium bromide (N 111.I4 Br) 5 Figure S15. 1 H NMR spectrum of N 111.I4 Br (400 MHz, CD 3 CN, 296 K). N,N,N-Trimethyl-N-(2-methoxyethyl)ammonium bromide (N 111.1O2 Br) 6 Figure S16. 1 H NMR spectrum of N 111.1O2 Br (400 MHz, CD 3 CN, 296 K). Diethyldimethylammonium bromide (N 1122 Br) 6 Figure S17. 1 H NMR spectrum of N 1122 Br (400 MHz, CD 3 CN, 296 K). N,N,N-Triethyl-N-methylammonium bromide (N 1222 Br) 6 Figure S18. 1 H NMR spectrum of N 1222 Br (400 MHz, CD 3 CN, 296 K). S8

9 N,N,N-Triethyl-N-propylammonium bromide (N 2223 Br) 6 Figure S19. 1 H NMR spectrum of N 2223 Br (400 MHz, CD 3 CN, 296 K). Diethyldipropylammonium bromide (N 2233 Br) 6 Figure S20. 1 H NMR spectrum of N 2233 Br (400 MHz, CD 3 CN, 296 K). S4. Synthesis of the self-assembled complexes [K([18]crown-6)] 12 [(PO 4 ) 4 (L) 4 ] [K([18]crown-6)] 3 (PO 4 ) (13 μl, mol/l; generated in situ from K 3 PO 4 and 18-Crown-6) was added to a suspension of L (10 mg, 8 μmol) in acetonitrile (1 ml). After stirring overnight at room temperature, a clear orange solution was obtained. Slow vapor diffusion of diethyl ether into this solution provided yellow crystals of [K([18]crown-6)] 12 [(PO 4 ) 4 (L) 4 ] within two weeks (yield >90%). 1 H NMR (400 MHz, DMSO-d 6, ppm): (s, 1H, NHd), (s, 1H, NHc), (s, 1H, NHb), (s, 1H, NHa), 8.27 (d, J = 8 Hz, 1H, H6), (5H, H1/2/3), 7.66 (d, J = 8 Hz, 2H, H8), 7.46 (d, 2H, J = 8 Hz, H7), 6.95 (m, 2H, H4/5). S9

10 Figure S21. 1 H NMR spectra of L and [K([18]crown-6)] 12 [(PO 4 ) 4 L 4 ] (400 MHz, DMSO-d 6, 296 K). Figure S22. Partial 1 H NMR spectrum of [K([18]crown-6)] 12 [(PO 4 ) 4 L 4 ] (400 MHz, CD 3 CN, 296 K). Figure S P NMR spectra of [K([18]crown-6)] 3 (PO 4 ) and [K([18]crown-6)] 12 [(PO 4 ) 4 L 4 ] (triphenylphosphine was used as internal standard; 162 MHz, CD 3 CN, 296 K). S10

11 (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] (3 TEA + ) (TEA) 3 PO 4 (13 μl, mol/l; generated in situ from (TEA)OH and H 3 PO 4 in water) was added to a suspension of L (10 mg, 8 μmol) in acetonitrile (1 ml). After stirring overnight at room temperature, a clear yellow solution was obtained. Slow vapor diffusion of diethyl ether into this solution provided yellow crystals of (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] within two weeks (yield >90 %). 1 H NMR (400 MHz, DMSO-d 6, ppm): (s, 1H, NHd), (d, 2H, NHb/NHc), (s, 1H, NHa), 8.78 (s, 1H, H1), 8.34 (s, 1H, H2), 8.23 (d-d, J = 8 Hz, 2H, H6/3), 7.68 (t, 3H, J = 8 Hz, H8/1), 7.56 (s, 1H, H2), 7.49 (d, J = 8 Hz, 2H, H7), 6.98 (m, 2H, H4/5). Figure S24. 1 H NMR spectrum of (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] (3 TEA + ) (400 MHz, DMSO-d 6, 296 K). (TPA) 12 [(PO 4 ) 4 (L) 4 ] (TPA) 3 PO 4 (13 μl, mol/l; generated in situ from (TPA)OH and H 3 PO 4 in water) was added to a suspension of L (10 mg, 8 μmol) in acetonitrile (1 ml). After stirring overnight at room temperature, a clear orange solution was obtained. Slow vapor diffusion of diethyl ether into this solution provided yellow crystals of (TPA) 12 [(PO 4 ) 4 (L) 4 ] within two weeks (yield >90 %). 1 H NMR (400 MHz, DMSO-d 6, ppm): (s, 1H, NHd), (s, 1H, NHc), (s, 1H, NHb), (s, 1H, NHa), 8.27 (d, J = 8 Hz, 1H, H6), (5H, H1/2/3), 7.66 (d, J = 8 Hz, 2H, H8), 7.46 (d, 2H, J = 8 Hz, H7), 6.95 (m, 2H, H4/5). S11

12 Figure S25. 1 H NMR spectrum of (TPA) 12 [(PO 4 ) 4 (L) 4 ] (400 MHz, DMSO-d 6, 296 K). (TBA) 12 [(PO 4 ) 4 (L) 4 CH 3 CN] (3 CH 3 CN) (TBA) 3 PO 4 (13 μl, mol/l; generated in situ from (TBA)OH and H 3 PO 4 in water) was added to a suspension of L (10 mg, 8 μmol) in acetonitrile (1 ml). After stirring overnight at room temperature, a clear yellow solution was obtained. Slow vapor diffusion of diethyl ether into this solution provided yellow crystals of (TBA) 12 [(PO 4 ) 4 (L) 4 CH 3 CN] within two weeks (yield >90 %). 1 H NMR (400 MHz, DMSO-d 6, ppm): (s, 1H, NHd), (s, 1H, NHc), (s, 1H, NHb), (s, 1H, NHa), 8.27 (d, J = 8 Hz, 1H, H6), (5H, H1/2/3), 7.66 (d, J = 8 Hz, 2H, H8), 7.46 (d, 2H, J = 8 Hz, H7), 6.95 (m, 2H, H4/5). Figure S26. 1 H NMR spectrum of (TBA) 12 [(PO 4 ) 4 (L) 4 CH 3 CN] (3 CH 3 CN) (400 MHz, DMSO-d 6, 296 K). S12

13 S5. Crystal structures of the guest-inclusion complexes Figure S27. Crystal structure of a) 3 CH 3 CN; b) schematic view of the weak interactions around the trapped CH 3 CN molecule; c) hydrogen bonds between the protons of the urea groups and PO 4 3 ; d) the six intramolecular hydrogen bonds associated with ligand L. Figure S28. Crystal structure of a) 3 TEA + ; b) schematic view of the weak interactions around the trapped TEA + molecule; c) hydrogen bonds between the protons of urea groups and PO 4 3 ; d) the six intramolecular hydrogen bonds associated with ligand L. S13

14 Figure S29. Space-filling view showing three of the peripheral TEA + counter cations associated with 3 TEA +. Figure S30. Crystal structure of a) 3 N ; b) schematic view of the weak interactions around the trapped N molecule; c) hydrogen bonds between the protons of the urea groups and PO 4 3 ; d) the six intramolecular hydrogen bonds associated with ligand L. S14

15 Figure S31. Schematic view of the crystal structures showing the vertical distances between the triazine plane and the triangle formed by three of the phosphorus atoms present in 3 CH 3 CN. Figure S32. Schematic view of the crystal structure showing the vertical distance between the triazine plane and the triangle formed by three of the phosphorus atoms present in 3 TEA +. Figure S33. Schematic view of the crystal structures showing the vertical distances between the triazine plane and the triangle formed by three of the phosphorus atoms present in 3 N S15

16 Figure S34. PO 4 3 PO 4 3 distances seen in cage 2 CH 3 CN. Figure S35. PO 4 3 PO 4 3 distances seen in a) 3 CH 3 CN; b) 3 TEA + and c) 3 N S6. 1 H and 2D NMR spectroscopy Figure S36. 1 H NMR spectra of cage 3 and cage 3 with 1 equiv TMA + (the signal of trapped TMA + is labeled in red, the blue area highlights the signals corresponding to H1 and H2; 400 MHz, CD 3 CN, 296 K). S16

17 Figure S37. 1 H NMR spectra of cage 3 and cage 3 with 1 equiv TEA + (the signals of trapped TEA + are labeled in red, while the blue highlighted areas are the signals corresponding to H1 and H2; 400 MHz, CD 3 CN, 296 K). Figure S38. 1 H NMR spectra of cage 3 and cage 3 recorded in the presence of 1 equiv of N (the signals of trapped N are labeled in red, while the blue highlighted area corresponds to the H1 and H2 signals; 400 MHz, CD 3 CN, 296 K). S17

18 Figure S39. 1 H NMR spectra of cage 3 and cage 3 with 1 equiv N (the signals of trapped N are shown in red, with the blue highlighted area representing the signals of H1 and H2; 400 MHz, CD 3 CN, 296 K). Figure S40. 1 H NMR spectra of cage 3 and cage 3 with 1 equiv N (the signals of trapped N are shown in red, with the blue highlighted area representing the signals of H1 and H2; 400 MHz, CD 3 CN, 296 K). S18

19 Figure S41. 1 H NMR spectra of cage 3 and cage 3 with 1 equiv N (the signals of trapped N are shown in red, with the blue highlighted area representing the signals of H1 and H2; 400 MHz, CD 3 CN, 296 K). Figure S42. 1 H NMR spectra of cage 3 and cage 3 with 1 equiv N (the signals of trapped N are shown in red, with the blue highlighted area representing the signals of H1 and H2; 400 MHz, CD 3 CN, 296 K). S19

20 Figure S43. 1 H NMR spectra of cage 3 and cage 3 with 2 equiv N (the signals of trapped N are shown in red, with the blue highlighted area representing the signals of H1 and H2; 400 MHz, CD 3 CN, 296 K). Figure S44. 1 H NMR spectra titration of cage 3 (1 mm) with N (the signals corresponding to the trapped N are shown in red; the signals of free N are in blue, while the blue highlight represent the signals of H1 and H2; 400 MHz, CD 3 CN, 296 K). S20

21 Figure S45. 1 H NMR spectra of cage 3 and cage equiv of N 111.1O2 + (the signals of free N 111.1O2 + are shown in blue; 400 MHz, CD 3 CN, 296 K). Figure S46. 1 H NMR spectra of cage 3 and cage equiv N (the signals of free N are shown in blue; 400 MHz, CD 3 CN, 296 K). S21

22 Figure S47. 1 H NMR spectra of cage 3 and cage equiv N 111.I4 + (the signals of free N 111.I4 + are shown in blue; 400 MHz, CD 3 CN, 296K). Figure S48. 1 H NMR spectra of cage 3 and cage equiv MeD + (the signals of trapped MeD + are shown in red, while the blue highlights correspond to the signals for H1 and H2; 400 MHz, CD 3 CN, 296 K). S22

23 Figure S49. 1 H NMR spectra of cage 3 and cage equiv MeDMe 2+ (the signals of free MeDMe 2+ are shown in blue; 400 MHz, CD 3 CN, 296 K). Figure S50. 1 H NMR spectra of cage 3 and cage 3 with 4 equiv ASN + (the signals of trapped ASN + are shown in red, the signals of free ASN + are in blue, while the blue shading corresponds to the signals for H1 and H2; 400 MHz, CD 3 CN, 296 K). S23

24 Figure S51. 1 H- 1 H COSY spectrum of (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] (3 TEA + ) (400 MHz, DMSO-d 6, 296 K). Figure S52. Partial 1 H- 1 H COSY spectrum of (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] (3 TEA + ) (400 MHz, DMSO-d 6, 296 K). S24

25 Figure S53. 1 H- 1 H NOESY spectrum of (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] (3 TEA + ) (400 MHz, DMSO-d 6, 296 K). Figure S54. Partial 1 H- 1 H NOESY spectra of (TEA) 11 [(PO 4 ) 4 (L) 4 TEA] (3 TEA + ) (400 MHz, DMSO-d 6, 296 K). Table S1. Selection of cationic guests for competition experiments. S25

26 Figure S55. 1 H NMR spectra of a) cage 3 TEA + ; b) cage 3 : TEA + : N = 1:1:1; c) cage 3 N (the signals of trapped TEA + are labeled in red while those for trapped N are labeled green; 400 MHz, CD 3 CN, 296 K). Figure S56. 1 H NMR spectra of a) cage 3 TEA + ; b) cage 3 : TEA + : MeD + = 1:1:1; c) cage 3 MeD + (the signals of trapped TEA + are labeled in red, while trapped MeD + are labeled in green; 400 MHz, CD 3 CN, 296 K). S26

27 Figure S57. 1 H NMR spectra of a) cage 3 TEA + ; b) cage 3 : TEA + : N = 1:1:1; c) cage 3 N (the signals of trapped TEA + are in red, while those for N are labeled in green; 400 MHz, CD 3 CN, 296 K). Figure S58. 1 H NMR spectra of a) cage 3 TEA + ; b) cage 3 : TEA + : TMA + = 1:1:1; c) cage 3 TMA + (the signals of trapped TEA + are labeled in red, while those for TMA + are labeled in green; 400 MHz, CD 3 CN, 296 K). S27

28 Figure S59. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : MeD + = 1:1:1; c) cage 3 MeD + (the signals of trapped N are red, while those for MeD + are labeled in green; 400 MHz, CD 3 CN, 296 K). Figure S60. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of trapped N are shown in red, while those for N are green; 400 MHz, CD 3 CN, 296 K). S28

29 Figure S61. 1 H NMR spectra of a) cage 3 MeD + ; b) cage 3 : MeD + : N = 1:1:1; c) cage 3 N (the signals of trapped MeD + are red, while those for N are green; 400 MHz, CD 3 CN, 296 K). Figure S62. 1 H NMR spectra of a) cage 3 MeD + ; b) cage 3 : MeD + : N = 1:1:1; c) cage 3 N (the signals of the trapped MeD + are shown in red, while those of N are in green; 400 MHz, CD 3 CN, 296 K). S29

30 Figure S63. 1 H NMR spectra of a) cage 3 MeD + ; b) cage 3 : MeD + : N = 1:1:1; c) cage 3 N (the signals of the trapped MeD + are shown in red, while those of N are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S64. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red, while those of N are shown in green; 400 MHz, CD 3 CN, 296 K). S30

31 Figure S65. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red, while those of N are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S66. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the rapped N are shown in red, while those of the N are shown in green; 400 MHz, CD 3 CN, 296 K). S31

32 Figure S67. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : TMA + = 1:1:1; c) cage 3 TMA + (the signals of the trapped N are shown in red color while those of TMA + are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S68. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red while those of N are shown in green; 400 MHz, CD 3 CN, 296 K). S32

33 Figure S69. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red, while those of N are green; 400 MHz, CD 3 CN, 296 K). Figure S70. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : TMA + = 1:1:1; c) cage 3 TMA + (the signals of the trapped N are shown in red, while those of TMA + are green; 400 MHz, CD 3 CN, 296 K). S33

34 Figure S71. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red, while those of N are green; 400 MHz, CD 3 CN, 296 K). Figure S72. 1 H NMR spectra of a) cage 3 TMA + ; b) cage 3 : TMA + : N = 1:1:1; c) cage 3 N (the signals of the trapped TMA + are shown in red, while those of N are green; 400 MHz, CD 3 CN, 296 K). S34

35 Figure S73. 1 H NMR spectra of a) cage 3 TMA + ; b) cage 3 : TMA + : N = 1:1:1; c) cage 3 N (the signals of the trapped TMA + are shown in red color, while those of N are green; 400 MHz, CD 3 CN, 296 K). Figure S74. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red while those of N are green; 400 MHz, CD 3 CN, 296 K). S35

36 Figure S75. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : ASN + = 1:1:1; c) cage 3 ASN + (the signals of the trapped N are shown in red, while those of ASN + are green; 400 MHz, CD 3 CN, 296 K). Figure S76. 1 H NMR spectra of a) cage 3 N ; b) cage 3 : N : N = 1:1:1; c) cage 3 N (the signals of the trapped N are shown in red, while those of N are green; 400 MHz, CD 3 CN, 296 K). S36

37 Figure S77. 1 H NMR spectra of a) cage 3 ASN + ; b) cage 3 : ASN + : N = 1:1:1; c) cage 3 N (the signals of the trapped ASN + are shown in red, while those of N are green; 400 MHz, CD 3 CN, 296 K). Figure S78. 1 H NMR spectra of a) cage 2 TMA + ; b) cage 2 : TMA + : TEA + = 1:1:1; c) cage 2 TEA + (the signals of the trapped TMA + are shown in red, while those of TEA + are green; 400 MHz, CD 3 CN, 296 K). S37

38 Figure S79. Partial 1 H NMR spectra of a) cage 2 TMA + ; b) cage 2 : cage 3 : TMA + = 1:1:1; c) cage 3 TMA + (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S80. Partial 1 H NMR spectra of a) cage 2 TEA + ; b) cage 2 : cage 3 : TEA + = 1:1:1; c) cage 3 TEA + (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S81. Partial 1 H NMR spectra of a) cage 2 N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). S38

39 Figure S82. Partial 1 H NMR spectra of a) cage 2 N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S83. Partial 1 H NMR spectra of a) cage 2 N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S84. Partial 1 H NMR spectra of a) cage 2 N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). S39

40 Figure S85. Partial 1 H NMR spectra of a) cage 2 N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S86. Partial 1 H NMR spectra of a) cage 2 with 1 equiv N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals corresponding to species trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S87. Partial 1 H NMR spectra of a) cage 2 with 1 equiv N ; b) cage 2 : cage 3 : N = 1:1:1; c) cage 3 N (signals corresponding to species trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). S40

41 Figure S88. Partial 1 H NMR spectra of a) cage 2 MeD + ; b) cage 2 : cage 3 : MeD + = 1:1:1; c) cage 3 MeD + (signals for species trapped by cage 2 are in red, whereas those trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). Figure S89. Partial 1 H NMR spectra of a) cage 2 with 1 equiv ASN + ; b) cage 2 : cage 3 : ASN + = 1:1:1; c) cage 3 ASN + (signals for species trapped by cage 3 are shown in green; 400 MHz, CD 3 CN, 296 K). S7. Isothermal titration calorimetry studies Figure S90. ITC data and curve fits for the titration of cage 3 (0.01 mm) in the cell with a solution of TEA + (0.1 mm) in the syringe in MeCN at 298 K. TEA + : cage 3 = 1:1. S41

42 Figure S91. ITC data and curve fits for the titration of cage 3 (0.5 mm) in the cell with a solution of TMA + (5 mm) in the syringe in MeCN at 298 K. TMA + : cage 3 = 1:1. Figure S92. ITC data and curve fits for the titration of cage 3 (0.2 mm) in the cell with a solution of N (3 mm) in the syringe in MeCN at 298 K. N : cage 3 = 1:1. S42

43 S8. Analysis of guest exchange For the HG 1+G2 HG 2+G1 equilibrium, the corresponding equilibrium constant (K rel ) calculations were made in accord with published procedures. 7 K rel [HG 2][G (HG 1] 2) [12 (HG 1)] [HG ][G ] (HG ) [12 (HG )] (HG 1 ), and (HG 2 ) represent the integration of the 1 H NMR signals corresponding to the trapped guests (G 1 : TMA +, G 2 : TEA + ). For integration details, see Figures S78 and S58). S9. High-resolution MS studies Figure S93. High-resolution ESI-mass spectrum of [K([18]crown-6)] 12 [(PO 4 ) 4 L 4 ]. S43

44 Figure S94. High-resolution ESI-mass spectrum of [TPA] 12 [(PO 4 ) 4 L 4 ]. Figure S95. High-resolution ESI-mass spectrum of 3 CH 3 CN. S44

45 Figure S96. High-resolution ESI-mass spectrum of 3 TMA +. Figure S97. High-resolution ESI-mass spectrum of 3 N S45

46 Figure S98. High-resolution ESI-mass spectrum of 3 N Figure S99. High-resolution ESI-mass spectrum of 3 N S46

47 Figure S100. High-resolution ESI-mass spectrum of 3 N Figure S101. High-resolution ESI-mass spectrum of 3 N S47

48 Figure S102. High-resolution ESI-mass spectrum of 3 MeD +. Figure S103. High-resolution ESI-mass spectrum of 3 ASN +. S48

49 Figure S104. High-resolution ESI-mass spectrum of a 1:1:1 mixture of cage 2 : TMA + : TEA +. The main signals belonging to 2 TMA + are shown in red, whereas those involving TEA + are in blue. Figure S105. High-resolution ESI-mass spectra of a 1:1:1 mixture of cage 3 : TMA + : TEA +. The main signals belong to 3 TEA + are shown in blue. S49

50 Figure S106. High-resolution ESI-mass spectra of the mixture of a 1:1:1:1 mixture of cage 2 : cage 3 : TMA + : TEA +. The main signals belonging to 2 TMA + are shown in red whereas those corresponding to 3 TEA + are shown in blue. S10. Studies of DABCO methylation Figure S H NMR spectra of a) 1 equiv of iodomethane added to DABCO; b) after this solution was heated for one hour at 50 C; c) spectrum after 9 equiv of iodomethane were added to the solution in b; d) spectrum recorded after the solution in c was heated at 50 C for another three hours. Color codes: Blue = MeD + ; red = MeDMe 2+ ; and purple = DABCO. Trioxane was used as the internal standard (400 MHz, CD 3 CN, 296 K). S50

51 Figure S H NMR spectra of a) spectrum recorded after adding 1 equiv of iodomethane to a solution of cage 3 and DABCO; b) spectrum recorded after this solution was heated at 50 C for one hour; c) spectrum recorded after adding 9 equiv of iodomethane to the solution in b; d) spectrum recorded after solution c was heated at 50 C for another three hours. Color codes: Blue = MeD + ; and purple = DABCO. Trioxane was used as the internal standard (400 MHz, CD 3 CN, 296 K). Figure S H NMR spectra of a) spectrum recorded after adding 10 equiv of iodomethane to a solution of cage 3 and DABCO and after the solution was heated at 50 C for four hours; b) spectrum recorded after adding 2 equiv of TEA + to this solution; c) spectrum recorded after the solution in b was heated at 50 C for one hour. Color codes: Blue = MeD + ; red = MeDMe 2+ ; and green = TEA +. Trioxane was used as the internal standard (400 MHz, CD 3 CN, 296 K). S51

52 S11. X-ray crystallography The diffraction data for 3 CH 3 CN and 3 TEA + were collected on a Bruker SMART APEX II diffractometer at 100 K with graphite-monochromated Cu-K radiation (λ = Å). The diffraction data of 3 N were collected on a Bruker D8 Venture TXS-Cu photon II diffractometer at 153 K with a Turbo X-Ray Source Cu-K radiation (λ = Å). An empirical absorption correction using SADABS was applied for all data. The structures of 3 CH 3 CN, 3 TEA + and 3 N were solved by the dual space method using the SHELXS program. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares on F 2 by the use of the SHELXL program. Hydrogen atoms bonded to carbon and nitrogen atoms were included in idealized geometric positions with thermal parameters equivalent to 1.2 times those of the atom to which they were attached. The remaining solvents could not be successfully resolved despite numerous attempts at modeling, and consequently the SQUEEZE function of PLATON was used to account for these highly disordered solvents. The removed void electron density corresponds to about water molecules for 3 CH 3 CN, 34.2 for 3 TEA + and for 3 N per cage. Except for the acetonitrile molecule in the center of cage 3, a Q peak was observed in the center of the cavity. Many attempts have been done to the model this residual Q peak. Finally, the Q peak was modelled to an O atom due to the similar electron density associated with this Q peak and a singled water molecule. Due to the moderate quality of the diffraction data for 3 N and 3 CH 3 CN, the counter cations could not be completely located. In addition, fourteen phenyl rings for 3 N , were refined with restraints. Three nitro groups in 3 N were refined with restraints. One C N bond for guest N in + 3 N 2223 and the C N bond of guest CH 3 CN in 3 CH 3 CN were refined with restraints. The counter cations (eight TBA + for 3 CH 3 CN, two TEA + for 3 TEA +, five TBA + for 3 CH 3 CN) were refined with restraints. CCDC contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via Table S2. Crystal data of 3 CH 3 CN, 3 TEA + and 3 N CH 3 CN 3 TEA N 2223 Empirical formula C 700 H 862 N 173 O 140 P 8 C H N O 40 P 2 C H N O 164 P 8 Formula weight Crystal System Monoclinic Orthorhombic Monoclinic Space group C2/c Fddd I2/a a (Å) (17) (6) (3) b (Å) (9) (14) (3) c (Å) (12) (3) (5) S52

53 α (deg) β (deg) (2) (3) γ (deg) V (Å 3 ) (5) 98208(5) 98045(12) Z D calc, g/cm No. of unique data T (K) 100(2) 100(2) 153(2) Total no. of data Crystal size (mm) θ range Completeness to θ 98.2% 96.6% 98.3 % Goodness-of-fit on F R wr Table S3. Hydrogen bonds around the PO 3 4 ions in 3 CH 3 CN. PO 4 D H A d(d H) d(h A) d(d A) (DHA) P1 N10 H10 O (3) 165 N11 H11 O (3) 166 N66 H66 O (4) 162 N43 H43A O (3) 169 N64 H64 O (4) 149 N65 H65 O (4) 167 N9 H9 O (3) 142 N40 H40A O (3) 143 N63 H63A O (3) 148 N12 H12 O (3) 168 N41 H41 O (3) 164 N42 H52 O (3) 166 S53

54 P2 N5 H5 O (3) 156 N6 H6 O (3) 162 N48 H48A O (4) 161 N7 H7 O (3) 165 N23 H23 O (4) 165 N24 H24 O (4) 167 N25 H25 O (4) 169 N46 H46A O (3) 152 N47 H47 O (4) 167 N4 H4 O (3) 143 N22 H22 O (3) 150 N45 H45A O (3) 144 P3 N35 H35 O (3) 167 N69 H69A O (4) 162 N70 H70 O (3) 167 N51 H51 O (5) 157 N52 H52A O (4) 166 N71 H71A O (5) 162 N33 H33 O (3) 165 N34 H34 O (3) 166 N53 H53A O (4) 160 N32 H32 O (3) 144 N50 H50 O (3) 155 N68 H68A O (3) 149 P4 N15 H15 O (3) 163 N16 H16 O (3) 166 N30 H30 O (3) 160 N14 H14 O (3) 136 N27 H27 O (3) 149 N58 H58 O (3) 143 N17 H17 O (3) 167 S54

55 N59 H59A O (3) 161 N60 H60A O (3) 164 N28 H28 O (3) 159 N29 H29 O (3) 168 N61 H61 O (4) 164 Table S4. Hydrogen bonds around the PO 3 4 ions in 3 TEA +. D H A d(d H) d(h A) d(d A) (DHA) N4 H4 O (2) 133 N9 H9A O (2) 142 N14 H14A O (2) 143 N5 H5A O (2) 162 N6 H6A O (2) 171 N12 H12A O (3) 171 N10 H10 O (2) 159 N11 H11 O (2) 164 N17 H17 O (2) 169 N7 H7 O (2) 166 N15 H15A O (2) 163 N16 H16 O (2) 170 Table S5. Hydrogen bonds around the PO 3 4 ions in 3 N PO 4 D H A d(d H) d(h A) d(d A) (DHA) P1 N4 H4 O (3) 148 N22 H22 O (3) 149 N50 H50 O (3) 147 N5 H5 O (3) 160 N6 H6 O (3) 165 N25 H25 O (3) 159 N7 H7 O (3) 168 N51 H51 O (3) 161 N52 H52 O (3) 166 N23 H23 O (3) 158 S55

56 N24 H24 O (3) 169 N53 H53 O (3) 168 P2 N48 H48 O (3) 154 N64 H64 O (3) 162 N65 H65 O (3) 167 N30 H30 O (3) 156 N46 H46 O (3) 163 N47 H47 O (15) 168 N27 H27 O (3) 149 N45 H45 O (3) 151 N63 H63 O (3) 149 N28 H28 O (3) 165 N29 H29 O (3) 164 N66 H66 O (3) 151 P3 N12 H12A O (3) 167 N59 H59 O (3) 162 N60 H60 O (3) 166 N41 H41 O (3) 157 N42 H42 O (4) 168 N61 H61 O (4) 166 N10 H10 O (3) 161 N11 H11 O (3) 167 N43 H43 O (3) 158 N9 H9A O (3) 148 N40 H40 O (3) 150 N58 H58 O (3) 143 P4 N17 H17 O (3) 167 N33 H33 O (3) 162 N34 H34 O (3) 164 N15 H15A O (3) 161 N16 H16 O (3) 165 S56

57 N71 H71A O (4) 162 N35 H35 O (4) 166 N69 H69A O (3) 159 N70 H70 O (4) 168 N14 H14A O (3) 147 N32 H32 O (3) 147 N68 H68A O (3) 151 S12. Volume calculations VOIDOO calculations based on the crystal structure were performed to determine the internal cavity volume of cage 3. Standard virtual probes of 1, 1.2, and 1.4 Å (set by default, water-sized) were used, as were standard parameters taken from published procedures Maximum number of volume-refinement cycles: 30 Minimum size of secondary grid: 3 Primary grid spacing: 0.1 Grid for plot files: 0.1 The cationic guests were optimized by DFT calculations with wb97xd functional and g** basis set and then the density volume was estimated with Iop (6/45=2000) in Gaussian 09 software package. Table S6. Volume calculations using different probes. Volume of cavities Size of probe 1 Å 1.2 Å 1.4 Å Cage 2 CH 3 CN 97 Å 3 87 Å 3 79 Å 3 Cage 2 TMA Å Å Å 3 Cage 2 No convergence No convergence 228 Å 3 (DFT optimized) Cage 3 CH 3 CN 150 Å Å Å 3 Cage 3 TEA Å Å 3 No convergence Cage 3 N Å Å Å 3 S57

58 Table S7. PO 4 3 PO 3 4 distances. distance (Å) min max average Cage 2 CH 3 CN Cage 2 TMA Cage (DFT optimized) Cage 3 CH 3 CN Cage 3 TEA Cage 3 N Figure S110. Cavity surface (gray) of 2 CH 3 CN drawn using PyMol. Figure S111. Cavity surface (gray) of 2 TMA + drawn using PyMol. S58

59 Figure S112. Cavity surface (gray) of 3 CH 3 CN drawn using PyMol. Figure S113. Cavity surface (gray) of 3 TEA + drawn using PyMol. Figure S114. Cavity surface (gray) of 3 N drawn using PyMol. S59

60 Figure S115. DFT optimized structures of the putative cationic guests used in this study. Figure S116. DFT optimized structures of free and trapped TEA +. S60

61 Figure S117. DFT optimized structures of free and trapped N S13. Supporting references (1) Ranganathan, A.; Heisen, B. C.; Dix, I.; Meyer, F. Chem. Commun. 2007, (2) Ishi-i, T.; Kuwahara, R.; Takata, A.; Jeong, Y.; Sakurai, K.; Mataka, S. Chem. Eur. J. 2006, 12, 763. (3) Marino, M. G.; Kreuer, K. D. ChemSusChem 2015, 8, 513. (4) Thomas, C.; Milet, A.; Peruch, F.; Bibal, B. Polym. Chem. 2013, 4, (5) Edson, J. B.; Macomber, C. S.; Pivovar, B. S.; Boncella, J. M. J. Membr. Sci. 2012, , 49. (6) Zhou, Z.-B.; Matsumoto, H.; Tatsumi, K. Chem. Eur. J. 2005, 11, 752. (7) Smulders, M. M. J.; Zarra, S.; Nitschke, J. R. J. Am. Chem. Soc. 2013, 135, (8) Riddell, I. A.; Smulders, M. M. J.; Clegg, J. K.; Nitschke, J. R. Chem. Commun. 2011, 47, 457. (9) Bolliger, J. L.; Ronson, T. K.; Ogawa, M.; Nitschke, J. R. J. Am. Chem. Soc. 2014, 136, (10) Castilla, A. M.; Ronson, T. K.; Nitschke, J. R. J. Am. Chem. Soc. 2016, 138, S61