Supplementary Information
Guest-dependent complexation of triptycene-derived macrotricyclic
host containing one anthracene moiety with paraquate derivatives:
construction of [2]rotaxanes
Ya-Kun Gu, Ying Han, and Chuan-Feng Chen*
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190, China.
Email: cchen@iccas.ac.cn
Contents
1. Copies of 1H NMR and 13C NMR of new compounds------------------------------S1
2. 1H NMR, 13C NMR and ROESY NMR spectra of [2]rotaxanes-----------------S5
3. 1H NMR titration experiments of the complex--------------------------------------S8
4. Mole ratio plots for the host and the guests of the complexes-------------------S10
5. ESI MS spectra of the complexes-----------------------------------------------------S13
6. Crystal packing of the complexes-----------------------------------------------------S16
7. Crystal data of the complexes----------------------------------------------------------S17
8. Ellipsoid plot for crystal structures of the complexes-----------------------------S21
S1
1. Copies of 1H NMR and 13C NMR of new compounds
Figure S1 1H NMR spectrum (CDCl3, 300 MHZ, 298k) of 3c.
Figure S2 13C NMR spectrum (CDCl3, 75 MHZ, 298k) of 3c.
S2
Figure S3 1H NMR spectrum (CDCl3, 300 MHZ, 298k) of 3d.
Figure S4 13C NMR spectrum (CDCl3, 75 MHZ, 298k) of 3d.
S3
Figure S5 1H NMR spectrum (CDCl3, 300 MHZ, 298k) of 2e.
Figure S6 13C NMR spectrum (CDCl3, 75 MHZ, 298k) of 2e.
S4
2. 1H NMR, 13C NMR and ROESY NMR spectra of [2]rotaxanes
Figure S7 1H NMR spectrum (CDCl3, 300 MHZ, 298k) of 4a
Figure S8 13C NMR spectrum (CDCl3, 75 MHZ, 298k) of 4a.
S5
Figure S9 1H NMR spectrum (CDCl3, 300 MHZ, 298k) of 4b.
Figure S10 13C NMR spectrum (CDCl3, 75 MHZ, 298k) of 4b.
S6
Figure S11. 1H-1H ROESY spectrum (600 MHz, CDCl3, 295 K) of rotaxane 4a.
Figure S12. 1H-1H ROESY spectrum (600 MHz, CDCl3, 295 K) of rotaxane 4b.
S7
3. 1H NMR spectroscopic titrations of the complexes
Binding studies by proton 1H NMR. Science binding was a fast exchange process,
the association constants were determined by titrating a solution (3.0 × 10−3 M) of
host 1 in CD3CN/CDCl3 (1:1, v/v) with the increased amount of a solution (0.3 M in
CD3CN) of guests. Deuterated acetonitrile was used as the lock, and TMS was
employed as the internal standard. Chemical shifts were reported in parts per million
(ppm). Fitting of chemical shifts of proton H1 of host 1 was performed a nonlinear
regression algorithm using MATLAB.
Figure S13. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3 = 1:1, v/v, 295K) of
(a) free host 1, (b) 1 and 1.0 equiv. of 2b, and (c) free guest 2b. [1]0 = 3.0 mM.
S8
Figure S14. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3 = 1:1, v/v, 295K) of
(a) free host 1, (b) 1 and 1.0 equiv. of 2c, and (c) free guest 2c. [1]0 = 3.0 mM.
Figure S15. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3 = 1:1, v/v, 295K) of
(a) free host 1, (b) 1 and 1.0 equiv. of 2d, and (c) free guest 2d. [1]0 = 3.0 mM.
S9
Figure S16. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3 = 1:1, v/v, 295K) of
(a) free host 1, (b) 1 and 1.0 equiv. of 2e, and (c) free guest 2e. [1]0 = 3.0 mM.
4. Mole ratio between the host and the guests of the complexes
Binding Studies by Proton 1H NMR
Since binding was a fast exchange process, the association constants were determined
by titrating a solution (3.0 × 10−3 M) of host 1 in CD3CN/CDCl3 (1:1, v/v) with the
increased amount of a solution (0.3 M in CD3CN) of guests. Deuterated acetonitrile
was used as the lock, and TMS was employed as the internal standard. Chemical
shifts were reported in parts per million (ppm). Fitting of chemical shifts of H1 proton
of host 1 was performed a nonlinear regression algorithm using MATLAB.
S10
2.5
2.0
R2=0.964
[1]/[2a]
1.5
1.0
R2=0.992
0.5
0.0
6.64
6.66
6.68
6.70
6.72
6.74
6.76
6.78
Chemical Shift of H1 on Host (ppm)
Figure S17. Mole ratio plot for the complexation between 1 and 2a in CD3CN/CDCl3
(1:1, v/v) at 295 K. [1]0 = 3.0 mM.
2.5
2.0
R2=0.940
[1]/[2b]
1.5
1.0
R2=0.988
0.5
0.0
6.66
6.68
6.70
6.72
6.74
6.76
6.78
Chemical Shift of H1 on Host (ppm)
Figure S18. Mole ratio plot for the complexation between 1 and 2b in CD3CN/CDCl3
(1:1, v/v) at 295 K. [1]0 = 3.0 mM.
S11
2.5
2.0
R2=0.975
[1]/[2c]
1.5
1.0
R2=0.987
0.5
0.0
6.60
6.65
6.70
6.75
Chemical Shift of H1 on Host (ppm)
Figure S19. Mole ratio plot for the complexation between 1 and 2c in CD3CN/CDCl3
(1:1, v/v) at 295 K. [1]0 = 3.0 mM.
2.5
2.0
R2=0.948
[1]/[2d]
1.5
1.0
R2=0.991
0.5
0.0
6.62
6.64
6.66
6.68
6.70
6.72
6.74
6.76
6.78
Chemical Shift of H1 on Host (ppm)
Figure S20. Mole ratio plot for the complexation between 1 and 2d in CD3CN/CDCl3
(1:1, v/v) at 295 K. [1]0 = 3.0 mM.
S12
2.5
2.0
R2=0.985
[1] / [2e]
1.5
1.0
R2=0.984
0.5
0.0
6.58
6.60 6.62 6.64 6.66 6.68 6.70 6.72 6.74
Chemical Shift of H1 on Host (ppm)
Figure S21. Mole ratio plot for the complexation between 1 and 2e in CD3CN/CDCl3
(1:1, v/v) at 295 K. [1]0 = 3.0 mM.
5. ESI MS spectra of the complexes
H+G1_140709094512 #16 RT: 0.15 AV: 1 NL: 1.39E7
T: FTMS {1,1} + p ESI Full ms [200.00-2000.00]
659.30499
R=25200
z=2
100
90
80
1095.46509
R=19500
z=1
Relative Abundance
70
60
50
40
30
20
927.16010
R=21200
z=1
559.22681
R=27300
z=2
1463.57410
R=16900
z=1
10
0
400
600
800
1000
1200
1400
m/z
Figure S22. ESI MS of a solution of 1 and 2a in acetonitrile.
S13
1600
1800
H+G2 #16-17 RT: 0.15-0.16 AV: 2 NL: 8.33E6
T: FTMS {1,1} + p ESI Full ms [200.00-2000.00]
673.32008
R=24557
z=2
100
1095.46443
R=18883
z=1
90
80
Relative Abundance
70
60
50
40
983.22185
R=20075
z=1
559.22661
R=27133
z=2
30
705.27756
R=23572
z=2
20
1491.60479
R=16163
z=1
1263.41822
R=17556
z=1
10
0
600
800
1000
1200
1400
1600
m/z
Figure S23. ESI MS of a solution of 1 and 2b in acetonitrile.
H+G4 #16 RT: 0.15 AV: 1 NL: 2.05E7
T: FTMS {1,1} + p ESI Full ms [200.00-2000.00]
673.32104
R=25000
z=2
100
90
1095.46619
R=19400
z=1
80
Relative Abundance
70
60
50
40
30
983.22333
R=20600
z=1
20
10
559.22742
R=27100
z=2
1491.60730
R=16700
z=1
1127.45581
R=19000
z=1
0
600
800
1000
1200
1400
1600
m/z
Figure S24. ESI MS of a solution of 1 and 2c in acetonitrile.
S14
1800
1800
H+G3 #17 RT: 0.16 AV: 1 NL: 5.49E6
T: FTMS {1,1} + p ESI Full ms [200.00-2000.00]
715.36664
R=24200
z=2
100
90
80
1095.46436
R=19500
z=1
Relative Abundance
70
60
50
827.31531
R=22200
z=2
40
30
20
10
559.22644
R=27000
z=2
1263.41797
R=17900
z=1
603.31006
R=26100
z=?
1476.00391
R=16500
z=2
1575.69800
R=16000
z=1
0
600
800
1000
1200
m/z
1400
1600
1800
Figure S25. ESI MS of a solution of 1 and 2d in acetonitrile.
H+G5 #496-509 RT: 2.38-2.44 AV: 14 NL: 1.62E5
T: FTMS + p ESI Full ms [500.00-2000.00]
825.86974
R=13813
z=2
100
90
1095.46694
R=12167
z=1
80
Relative Abundance
70
60
50
40
1127.45664
R=12102
z=1
30
1439.64136
R=10684
z=1
20
1796.70541
R=9451
z=1
1378.10427
R=10892
z=2
10
0
800
900
1000
1100
1200
1300
1400
m/z
1500
1600
1700
1800
Figure S26. ESI MS of a solution of 1 and 2e in acetonitrile.
S15
1900
2000
6. Crystal packing of the complexes
Figure S27. Crystal packing of complex 1·2c. PF6- counterions and hydrogen atoms
were omitted for clarity.
Figure S28. Crystal packing of complex 1·2d. PF6- counterions and hydrogen atoms
were omitted for clarity.
S16
7. Crystal data of the complexes
Table S1. Crystal data for 1·2a.
Identification code
1·2a
Empirical formula
C111 H88 Cl3 F12 N2 O20 P2
Formula weight
2166.13
Temperature
173(2) K
Wavelength
0.71073 Å
Crystal system, space group
monoclinic, C 2/c
Unit cell dimensions
a = 37.089(7)Åalpha = 90.00 ˚
b = 16.922(3)Å beta = 112.86(3)˚
c = 42.559(8) Å gamma = 90.00˚
Volume
24613(8)Å3
Z, Calculated density
8, 1.169 Mg/m3
Absorption coefficient
0.179 mm-1
F(000)
8936
Crystal size
0.26×0.20×0.06 mm
Theta range for data collection
0.965 to 27.49˚
Limiting indices
-22<=h<=23, -25<=k<=26, -27<=l<=26
Reflections collected / unique
20004/ 28158 [R(int) = 0.3238]
Completeness to theta = 25.00
99.7 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
1.0000 and 0.318
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
28158/1253/1075
Goodness-of-fit on F2
2.831
Final R indices [I>2sigma(I)]
R1 = 0.3238,wR2= 0.5986
R indices (all data)
R1 = 0.3594, wR2 = 0.6126
Largest diff. peak and hole
1.732 and -0.875 e.Å-3
S17
Table S2. Crystal data for 1·2c.
Identification code
1·2c
Empirical formula
C94 H116 F24 N4 O20 P4
Formula weight
2201.79
Temperature
173(2) K
Wavelength
0.71073 Å
Crystal system, space group
triclinic, P-1
Unit cell dimensions
a = 12.143(2) Åalpha = 91.55(3) ˚
b = 17.646(4) Å beta = 98.23(3)˚
c = 24.394(5) Å gamma = 90.22(3) ˚
Volume
5171.2(18)Å3
Z, Calculated density
2, 1.414 Mg/m3
Absorption coefficient
0.184 mm-1
F(000)
2288
Crystal size
0.49×0.37×0.05 mm
Theta range for data collection
0.914to 25.00˚
Limiting indices
-14<=h<=14, -20<=k<=20, -29<=l<=28
Reflections collected / unique
13059/ 18219 [R(int) = 0.1019]
Completeness to theta = 25.00
99.9 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
1.0000 and 0.564
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
18219/2222/1470
Goodness-of-fit on F2
1.073
Final R indices [I>2sigma(I)]
R1 = 0.1019,wR2= 0.2654
R indices (all data)
R1 = 0.1314, wR2 = 0.2894
Largest diff. peak and hole
2.834 and -1.275 e.Å-3
S18
Table S3. Crystal data for 1·2d.
Identification code
1·2d
Empirical formula
C116 H138 F18 N6 O28 P3
Formula weight
2499.23
Temperature
173(2) K
Wavelength
0.71073 Å
Crystal system, space group
monoclinic, P2(1)/c
Unit cell dimensions
a = 16.687(4)Åalpha = 90.00 ˚
b = 27.990(5)Å beta = 106.10(3)˚
c = 27.480(6) Å gamma = 90.00˚
Volume
12332(4)Å3
Z, Calculated density
4, 1.346 Mg/m3
Absorption coefficient
0.149 mm-1
F(000)
5228
Crystal size
0.24×0.23×0.04 mm
Theta range for data collection
0.965 to 25.00˚
Limiting indices
-15<=h<=16, -49<=k<=49, -31<=l<=31
Reflections collected / unique
13985/21622 [R(int) = 0.1440]
Completeness to theta = 25.00
99.6 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
1.0000 and 0.318
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
21622/105/1555
Goodness-of-fit on F2
1.737
Final R indices [I>2sigma(I)]
R1 = 0.1440,wR2= 0.3403
R indices (all data)
R1 = 0.1878, wR2 = 0.3608
Largest diff. peak and hole
2.834 and -1.275 e.Å-3
S19
Table S4. Crystal data for 1·2e.
Identification code
1·2e
Empirical formula
C84 H106 F12 N2 O18 P2
Formula weight
1721.65
Temperature
173(2) K
Wavelength
0.71073 Å
Crystal system, space group
monoclinic, C 2/c
Unit cell dimensions
a = 41.280(8) Åalpha = 90.00 ˚
b = 16.774(3) Å beta = 120.74(3)˚
c = 32.671(7) Å gamma = 90.00˚
Volume
19444(9)Å3
Z, Calculated density
8, 1.176 Mg/m3
Absorption coefficient
0.127 mm-1
F(000)
7248
Crystal size
0.45×0.38×0.27 mm
Theta range for data collection
0.944 to 25.00˚
Limiting indices
-49<=h<=39, -19<=k<=19, -38<=l<=38
Reflections collected / unique
12867/ 17105 [R(int) = 0.1353]
Completeness to theta = 25.00
99.8 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
1.0000 and 0.478
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
17105/1467/1069
Goodness-of-fit on F2
2.269
Final R indices [I>2sigma(I)]
R1 = 0.1353,wR2= 0.3531
R indices (all data)
R1 = 0.1511, wR2 = 0.3643
Largest diff. peak and hole
2.256 and -1.113 e.Å-3
S20
8. Ellipsoid plot for crystal structures of the complexes
Figure S29．Ellipsoid plot for crystal structure of complex 1·2a with probability level
of 50%. Solvent molecules, and PF6- counterions were omitted for clarity.
Figure S30．Ellipsoid plot for crystal structure of complex 1·2c with probability level
of 50%. Solvent molecules, and PF6- counterions were omitted for clarity.
S21
Figure S31．Ellipsoid plot for crystal structure of complex 1·2d with probability level
of 50%. Solvent molecules, and PF6- counterions were omitted for clarity.
Figure S32．Ellipsoid plot for crystal structure of complex 1·2e with probability level
of 50%. Solvent molecules, and PF6- counterions were omitted for clarity.
S22