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 S2-S4Configuration Changes and Guest→Solvent Exchange

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 0lnln AktA (1)

kteAA 0 (2)

(3)

Eyring-Polanyi Equation

(4)

S8

k

t 2ln2

1

RT

‡G

B ehTkk

ln ( kT )=− ΔH ‡

RT+ ln

k B

h+ ΔS ‡

R

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

0 24 48 72 168 264 336 432 504 672 840a 3.76 3.68 3.52 3.31 2.83 2.18 2.04 0.92 0.73 0.56 0b 8.38 7.64 6.85 5.98 5.04 3.59 3.3 1.59 0.79 0.34 0c 24 24 24 24 24 24 24 24 24 24 24

Time in hours

Figure S13. Peaks a and b were normalized to peak c and used for kinetics calculations.

0 200 400 600 8000.0

0.5

1.0

Hours0 200 400 600 800

0.0

0.5

1.0

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

0 0.5 1 2 3 4 5 6 7 8 9 10 12 15 19 23 28 36 44 54 64 74a 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 0.52b 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 1.13 0.84 0.96 0.58c 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 3.49 3.12 3.16 2.6 1.81 0.76 0.78 0.34 0.55d 6.09 5.23 4.6 4.74 4.75 4.4 4.3 4.75 5.13 5.24 3.78 4.3 2.79 3.64 2.55 1.64 1.47 1.21 1.51 1.36 0.23 -0.31e 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24

f 5.19 5.3 4.44 3.99 4.72 5.34 4.63 3.96 5.51 3.57 3.05 4.03 2.57 2.8 3.23 2.19 1.98 2.09 1.37 1.38 0.66 1.2

Time in hours

S10

Figure S16. Peaks a-d and f were normalized to peak e and used for kinetics calculations.

0 20 40 60

0.0

0.5

1.0

Hours

0 20 40 60

0.0

0.5

1.0

Hours

Figure S17. First order kinetics plot for peak b Figure S18. First order kinetics plot for peak c

Fluorene Complex

Table S3: Integrated peak values for fluorene filled capsule in C6H12 for kinetics calculations. T = 323K

0 1 2 4 6 10 14 18 22 26 30 34 38 46 54 68.5a 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 1.44b 8.34 7.9 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 0.76c 8.54 9.23 8.67 6.72 6.75 5.76 4.64 4.48 3.2 2.57 2.25 1.42 1.53 2.21 2.15 1.91d 7.5 6.85 6.51 4.99 5.44 4.56 3.2 3.62 2.34 1.27 2 1.4 0.9 1.89 1.01 0.7

e 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24

Time in hours

S11

Figure S19. Peaks a-d were normalized to peak e and used for kinetics calculations.

0 20 40 60

0.0

0.5

1.0

Hours0 20 40 60

0.0

0.5

1.0

Hours

Figure S20. First order kinetics plot for peak b Figure S21. First order kinetics plot for peak d

S12

Norbornene Complex

Table S4: Integrated peak values for norbornene filled capsule in C6H12 for kinetics calculations. T = 323K

0 1 2 4 6 10 14 18 22 26 30 34 38 42 46 54 68.5a 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24b 10.3 7.92 6.9 6.6 4.57 5.97 4.02 4.52 4.16 3.32 2.32 2.76 2.79 1.67 2.87 1.94 1.28c 12.5 11.6 12.5 10.8 9.42 7.95 8.22 7.28 5.91 5.2 5.5 4.45 3.69 3.78 3.14 1.57 1.68d 3.14 3.52 3.34 3.4 3.32 2.55 3.12 2.33 2.66 1.8 1.97 1.77 1.3 1.17 1.7 0.43 0.51

Time in hours

Figure S22. Peaks b-d were normalized to peak a and used for kinetics calculations.

0 20 40 60

0.0

0.2

0.4

0.6

0.8

1.0

Hours0 20 40 60

0.2

0.4

0.6

0.8

1.0

Hours

Figure S23. First order kinetics plot for peak b Figure S24. First order kinetics plot for peak c

S13

Pyrene Complex

Table S5: Integrated peak values for pyrene filled capsule in C6H12 for kinetics calculations. T = 343K

0 0.5 1 2 3 4 5 6 7 8 9 10 12 15 19 23 28 36 44 54 64 74a 18.0 17.9 15.3 12.0 9.6 5.2 4.5 4.7 3.2 3.4 2.0 1.3 1.8 0.2 0.0 0.1 0 0 0 0 0 0b 5.0 4.9 6.0 8.8 10.2 11.5 12.0 12.5 12.9 12.9 12.9 12.1 12.2 10.9 9.0 7.8 6.0 4.8 4.6 2.2 1.9 1.0c 0.7 1.1 2.6 3.3 4.3 7.2 7.4 6.8 7.9 7.7 9.1 10.6 10.2 12.8 14.8 16.4 17.5 18.8 19.2 21.5 22.2 22.7

Time in hours

Figure S25. Peaks A-C were normalized to 24 over the range of 7.26-7.61ppm and used for kinetics calculations.

S14

Figure S26. Screen shot of KinTekSim line fitting for the data of the pyrene complex dissolved in C6H12. 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.

S15