Supplementary Information for:
Guest loading, chromatographic purification, and controlled release
from kinetically trapped, hydrogen-bonded pyrogallol[4]arene
capsules
Jennifer C. Chapina and Byron W. Pursea,b,*
a
Department of Chemistry and Biochemistry, University of Denver, 2199 S. University Blvd., Denver, CO, 80208, USA.
b
Department of Chemistry and Biochemistry, San Diego State University, 5500 Campanile Dr., San Diego, CA, 92182, USA. E-mail:
bpurse@mail.sdsu.edu
Table of Contents
1.
Stacked NMR Spectra for Bound Guests in Cyclohexane Showing Time Dependent
Configuration Changes and Guest→Solvent Exchange
S2-S4
2.
NMR Plots of Capsule Stability during Sonication Study
S4-S5
3.
NMR Plots for GPC Purified Guest-Filled Hexamers
S5-S7
4.
Kinetics Studies Description
S8
5.
First Order Kinetics Equations
S8
6.
Eyring-Polanyi Equations
S8
7.
Data Tables, Peak Identifications, and Kinetics Plots for Kinetics Measurements
S9-S14
S1
Stacked NMR Spectra for Bound Guests in C6H12 Showing Time Dependent Configuration Changes and
Guest→Solvent Exchange
Figure S1: Stacked plot of decylpyrogallolarene–anthracene complex in cyclohexane (C6H12).
Time is in hours. (1mM, 500MHz, 296K)
Figure S2: Stacked plot of decylpyrogallolarene–fluoranthene complex in C6H12.
Time is in hours. (1mM, 500MHz, 343K)
S2
Figure S3: Stacked plot of decylpyrogallolarene–fluorene complex in C6H12.
Time is in hours. (1mM, 500MHz, 323K)
Figure S4: Stacked plot of decylpyrogallolarene–norbornene complex in C6H12.
Time is in hours. (1mM, 500MHz, 323K)
S3
Figure S5: Stacked plot of decylpyrogallolarene–pyrene complex in C6H12.
Time is in hours. (1mM, 500MHz, 343K)
NMR Plots of Capsule Stability during Sonication Study
Figure S6: Stacked plot of decylpyrogallolarene–pyrene complex in CDCl3.
Sonication time given. (1mM, 500MHz, 296K)
S4
Figure S7: Overlay plot of initial decylpyrogallolarene–pyrene complex in CDCl3 and after 15 minutes of
sonication. (1mM, 500MHz, 296K)
NMR Plots for GPC Purified Guest-Filled Hexamers
Figure S8: Stacked plot of GPC purified decylpyrogallolarene–anthracene complex in cyclohexane (C6H12).
S5
Figure S9: Stacked plot of GPC purified decylpyrogallolarene–fluoranthene complex in cyclohexane (C6H12).
Figure S10: Stacked plot of GPC purified decylpyrogallolarene–fluorene complex in cyclohexane (C6H12).
S6
Figure S11: Stacked plot of GPC purified decylpyrogallolarene–norbornene complex in cyclohexane (C6H12).
Figure S12: Stacked plot of GPC purified decylpyrogallolarene–pyrene complex in cyclohexane (C6H12).
S7
Kinetics Studies Description
All guest exchange processes were found to follow kinetics that are first-order in capsule. NMR peaks
corresponding to the guest-filled capsule were integrated, normalized, and then used in non-linear curve fitting by
regression to determine the first-order rate constant, k. The peaks that were used for quantification and calibration
are labeled on the following spectra and integral values for each peak are given in the following tables. Example
first-order kinetics plots are given for each measurement. In the case of pyrene where the mechanism was more
complex than simple first-order kinetics (Table S5), KinTekSim was used to perform regression-based curve fitting
to determine k values. The mechanisms used for these cases are provided along with the data tables. All samples
were measured using a 500MHz NMR spectrometer at 296K.
First Order Kinetics Equations
ln A  kt  ln A0
(1)
A  A0ek t
(2)
ln 2
k
(3)
t1 
2
Eyring-Polanyi Equation
 G‡ 


 T   RT 
k   k B e  
 h
(4)
S8
Data Tables, Peak Identifications, and Kinetics Plots for Kinetics Measurements
Anthracene Complex
Table S1: Integrated peak values for anthracene filled capsule in C6H12 for kinetics calculations. T = 296K
Time in hours
0
24
48
72
168
264
336
432
504
672
840
a
3.76 3.68 3.52 3.31 2.83 2.18 2.04 0.92 0.73 0.56
0
b
8.38 7.64 6.85 5.98 5.04 3.59
0
c
24
24
24
24
24
24
3.3
1.59 0.79 0.34
24
24
24
24
24
Figure S13. Peaks a and b were normalized to peak c and used for kinetics calculations.
1.0
1.0
0.5
0.5
0.0
0.0
0
200
400
600
800
0
Hours
200
400
600
800
Hours
Figure S14. First order kinetics plot for peak a
Figure S15. First order kinetics plot for peak b
S9
Fluoranthene Complex
Table S2: Integrated peak values for fluoranthene filled capsule in C6H12 for kinetics calculations. T = 343K
Time in hours
0
0.5
1
2
3
4
5
6
7
8
9
10
12
15
19
23
28
36
44
54
64
74
a
6.44 5.54 7.49 5.56 5.36 5.47 4.23 5.81 5.71 5.08 5.43 5.51 5.15 4.87 6.03 5.17 4.37 2.59 2.01 0.77 0.41 0.52
b
6.14 5.36 7.32 5.08 4.62 4.64 4.16 5.04 3.84 3.78 4.27 3.99 3.11 3.16 3.04 3.41 2.28
1.9
c
6.32 4.97 6.96 4.52 4.56 4.41 4.15 4.99 4.29 4.08 4.56 4.45
3.3
1.81 0.76 0.78 0.34 0.55
d
6.09 5.23
2.79 3.64 2.55 1.64 1.47 1.21 1.51 1.36 0.23 -0.31
e
24
24
f
5.19
5.3
4.6
24
4.74 4.75
24
24
4.4
4.3
24
24
4.75 5.13 5.24 3.78
24
24
24
24
4.3
24
3.49 3.12 3.16
24
24
4.44 3.99 4.72 5.34 4.63 3.96 5.51 3.57 3.05 4.03 2.57
2.8
24
24
2.6
24
1.13 0.84 0.96 0.58
24
24
24
24
3.23 2.19 1.98 2.09 1.37 1.38 0.66
Figure S16. Peaks a-d and f were normalized to peak e and used for kinetics calculations.
1.0
1.0
0.5
0.5
0.0
0.0
0
20
40
60
0
Hours
20
40
60
Hours
Figure S17. First order kinetics plot for peak b
Figure S18. First order kinetics plot for peak c
S10
24
1.2
Fluorene Complex
Table S3: Integrated peak values for fluorene filled capsule in C6H12 for kinetics calculations. T = 323K
Time in hours
0
1
2
4
6
10
14
18
22
26
30
34
38
46
54
68.5
a
7.8
7.67 6.63 6.72 5.98 6.32 5.41 5.17 4.04 2.98 3.73 3.24 3.17 2.82 1.86 1.44
b
8.34
7.9
c
8.54 9.23 8.67 6.72 6.75 5.76 4.64 4.48
d
7.5
e
24
7.47 6.06 5.75 4.49 3.44 3.89 2.73 2.12 1.31 0.88 0.77 1.43 1.18 0.76
6.85 6.51 4.99 5.44 4.56
24
24
24
24
24
3.2
3.2
2.57 2.25 1.42 1.53 2.21 2.15 1.91
3.62 2.34 1.27
24
24
24
24
2
1.4
0.9
24
24
24
1.89 1.01
24
24
0.7
24
Figure S19. Peaks a-d were normalized to peak e and used for kinetics calculations.
1.0
1.0
0.5
0.5
0.0
0.0
0
20
40
60
0
Hours
20
40
60
Hours
Figure S20. First order kinetics plot for peak b
S11
Figure S21. First order kinetics plot for peak d
Norbornene Complex
Table S4: Integrated peak values for norbornene filled capsule in C6H12 for kinetics calculations. T = 323K
Time in hours
0
1
2
4
6
10
14
18
22
26
30
34
38
42
46
54 68.5
a
24
24
24
24
6.9
6.6
24
24
24
24
24
24
24
24
b
10.3 7.92
c
12.5 11.6 12.5 10.8 9.42 7.95 8.22 7.28 5.91
5.2
5.5
d
3.14 3.52 3.34
1.8
1.97 1.77
3.4
24
24
24
24
4.57 5.97 4.02 4.52 4.16 3.32 2.32 2.76 2.79 1.67 2.87 1.94 1.28
3.32 2.55 3.12 2.33 2.66
4.45 3.69 3.78 3.14 1.57 1.68
1.3
1.17
1.7
0.43 0.51
Figure S22. Peaks b-d were normalized to peak a and used for kinetics calculations.
1.0
1.0
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.0
0
20
24
40
60
0
Hours
20
40
60
Hours
Figure S23. First order kinetics plot for peak b
Figure S24. First order kinetics plot for peak c
S12
Pyrene Complex
Table S5: Integrated peak values for pyrene filled capsule in C6H12 for kinetics calculations. T = 343K
a
b
c
0
18.0
5.0
0.7
Time in hours
0.5 1
2
3
4
5
6
7
8
9 10
17.9 15.3 12.0 9.6 5.2 4.5 4.7 3.2 3.4 2.0 1.3
4.9 6.0 8.8 10.2 11.5 12.0 12.5 12.9 12.9 12.9 12.1
1.1 2.6 3.3 4.3 7.2 7.4 6.8 7.9 7.7 9.1 10.6
12
1.8
12.2
10.2
15
0.2
10.9
12.8
19
0.0
9.0
14.8
23 28 36 44 54 64 74
0.1 0
0
0
0
0
0
7.8 6.0 4.8 4.6 2.2 1.9 1.0
16.4 17.5 18.8 19.2 21.5 22.2 22.7
Figure S25. Peaks A-C were normalized to 24 over the range of 7.26-7.61ppm and used for kinetics calculations.
S13
Figure S26. Screen shot of KinTekSim line fitting for the data of the pyrene complex dissolved in C 6H12. Blue is
initial configuration green is second configuration, cyan is solvent filled capsule. Concentrations for each species
were determined from integrated and normalized 1NMR peaks and the initial concentration of the sample (1mM).
Mechanism used was initial configuration→second configuration→solvent-filled. Rate constants k1 (initial
configuration→second configuration) and k2 (second configuration→solvent-filled) were fit, k-1 and k-2 were set to
zero.
S14