Pyrogallol[4]arenes as frustrated organic solids

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1 Supporting Information Pyrogallol[4]arenes as frustrated organic solids Harshita Kumari, a Loredana Erra, b Alicia C. Webb, a Prashant Bhatt, c Charles L. Barnes, a Carol A. Deakyne, * a John E. Adams * a Leonard J. Barbour* b and Jerry L. Atwood* a a Department of Chemistry, University of Missouri-Columbia, 601 South College Avenue, Columbia, MO 65211, USA, b European Synchrotron Radiation Facility, 8 Rue J. Horowitz, Grenoble, France, c Department of Chemistry, University of Stellenbosch, 2002 Inorganic Chemistry Building, Stellenbosch, 7600, South Africa. Figure 1. Space filling representations of forms I (left) and II (right) show solvent-occupied volumes of 13.6% and 6.6%, respectively... 3 Figure 2. Packing diagrams of interdigitated heads and tails of self-included dimers of form I of PgC 5 with solvent (3 methanols) inclusion between alternate dimers Figure 3. Packing arrangement with interdigitated tails of form II of PgC 5 and heads showing channels of solvent inclusion Figure 4. Hirshfeld surface analyses of form I of PgC 5 showing surface charge of solvent inclusion showing Volume: Å 3 ; Area: Å 2 ; Globularity: 0.509; Aspehricity: Figure 5. Hirshfeld surface analyses of form I of PgC 5 showing surface charge of solvent inclusion showing Volume: Å 3 ; Area: Å 2 ; Globularity: 0.495; Aspehricity: Figure 6. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form... 6 Figure 7. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form: H...H dispersion interaction... 7 Figure 8.. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form: X H...O dispersion interaction... 8 Figure 9.. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form: X H... л dispersion interaction... 9 Figure 10.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form Figure 11.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form: H...H interaction Figure 12.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form: X H...O dispersion interaction Figure 13.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form: X H....л dispersion interaction Figure 14.DSC curve of PgC5: form II S1

2 Figure 15. PXRD curve from top to bottom: form I (magenta), form II (navy), form III (blue), form IV (brown), form V (red), form VI (purple), form VII (olive) Figure 16. Variable temperature PXRD curves of form II at 50 bar CO 2 pressure and at temperatures ranging from 25 C to 210 C. The color codes are given from top to bottom: 25 C (red), form II at 35 C (blue), form II at 45 C (green), form II at 55 C (grey), form II at 65 C (brown), form II at 75 C (turquoise), form II at 85 C (purple), form II at 95 C (yellow), form II at 110 C (red), form II at 130 C (blue), form II at 150 C (green), form II at 170 C (grey), form II at 190 C (brown), form II at 210 C (turquoise) Figure 17.CO 2 gas Sorption data of PgC 5 (form I & II) at 27atm/RT Figure 18.CO 2 gas sorption data of heat treated form IV of PgC 5 (form IV) Figure 19.CO 2 gas sorption data of solvated mixture (form I and II) of PgC S2

3 Simulation Protocol Molecular dynamics (MD) simulations were carried out using the gaff force field 1,2 as implemented within the AMBER program package 3. (Requisite atom-centered RESP partial charges 4,5 were generated from HF/6-31G(d) electronic structures obtained using Gaussian ) Our simulation protocols were those used previously in the study of calixarene host-guest complexes 7,8 ; thus, our analyses are based on NVE trajectories, the initial conditions for which were obtained via an NVT equilibration (and in the case of solvated species discussed below, an intermediate NPT step for equilibration of the solvent density). In addition, we generated the potential of mean force 9 for binding of a dimeric capsule using umbrella sampling and the weighted-histogram analysis method 10,11 (WHAM), the reaction path being defined here as the distance between the centers-of-mass of the four carbons at the lower rim of each pyrogallol[4]arene macrocycle. Packing Arrangement Figures Figure 1. Space filling representations of forms I (left) and II (right) show solvent-occupied volumes of 13.6% and 6.6%, respectively S3

4 Figure 2. Packing diagrams of interdigitated heads and tails of self-included dimers of form I of PgC 5 with solvent (3 methanols) inclusion between alternate dimers. Figure 3. Packing arrangement with interdigitated tails of form II of PgC 5 and heads showing channels of solvent inclusion. S4

5 Hirshfeld surface interaction figures (ASU): Figure 4. Hirshfeld surface analyses of form I of PgC 5 showing surface charge of solvent inclusion showing Volume: Å 3 ; Area: Å 2 ; Globularity: 0.509; Aspehricity: Figure 5. Hirshfeld surface analyses of form I of PgC 5 showing surface charge of solvent inclusion showing Volume: Å 3 ; Area: Å 2 ; Globularity: 0.495; Aspehricity: S5

6 Hirshfeld surface interaction figures (packing arrangement): NOTE: Needle: packing index (percent filled space) 68.7 (calculated with Platon-Kitaigorodskii type of packing index) 12 Plate: packing index (percent filled space) 66.8 (calculated with Platon-Kitaigorodskii type of packing index) 12 For both the structures, the solvent molecules have been included in the calculation; for the plate form the disorder is not considered. Figure 6. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form S6

7 Figure 7. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form: H...H dispersion interaction S7

8 Figure 8.. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form: X H...O dispersion interaction S8

9 Figure 9.. Hirshfeld surface analysis of packing arrangement of PgC 5 plate form: X H... л dispersion interaction S9

10 Figure 10.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form Figure 11.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form: H...H interaction S10

11 Figure 12.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form: X H...O dispersion interaction Figure 13.Hirshfeld surface analysis of packing arrangement of PgC 5 needle form: X H....л dispersion interaction S11

12 PXRD, DSC and Gas Sorption curves Figure 14.DSC curve of PgC5: form II NOTE: DSC curve for form II demonstrates distinct solvent loss at ~85 C and ~95 C Figure 15. PXRD curve from top to bottom: form I (magenta), form II (navy), form III (blue), form IV (brown), form V (red), form VI (purple), form VII (olive). S12

13 Figure 16. Variable temperature PXRD curves of form II at 50 bar CO 2 pressure and at temperatures ranging from 25 C to 210 C. The color codes are given from top to bottom: 25 C (red), form II at 35 C (blue), form II at 45 C (green), form II at 55 C (grey), form II at 65 C (brown), form II at 75 C (turquoise), form II at 85 C (purple), form II at 95 C (yellow), form II at 110 C (red), form II at 130 C (blue), form II at 150 C (green), form II at 170 C (grey), form II at 190 C (brown), form II at 210 C (turquoise) S13

14 Figure 17.CO 2 gas Sorption data of PgC 5 (form I & II) at 27atm/RT NOTE: The amount of CO 2 sorbed by a mixture of forms I and II (vacuum/rt treated for 6 hours) is ~12 wt% wt% of CO2 sorbed by form III of PgC5 Wt. % Pressure in atm Figure 18.CO 2 gas sorption data of heat treated form IV of PgC 5 (form IV) NOTE: The gas sorption study of heat-treated form IV shows that the new form sorbs ~1.1 wt% CO 2 (RT) S14

15 wt % wt% of CO2 sorbed by form I and II (solvated) of PgC Pressure in atm Figure 19.CO 2 gas sorption data of solvated mixture (form I and II) of PgC 5 Note: The solvated form sorbed only 1.5 wt% CO 2, and the CO 2 treated mixture indicates that a new form III is obtained REFERENCES: (1 ) Wang, J.; Wolf, R. M.; Caldwell, J. W.; Kollman, P. A.; Case, D. A. J Comput Chem 2004, 25, (2) Wang, J.; Wolf, R. M.; Caldwell, J. W.; Kollman, P. A.; Case, D. A. J. Comput. Chem , 114. (3) Case, D. A. D., T. A.; Cheatham, T. E., III; Simmerling, C. L.; Wang, J.; Duke, R. E.; Luo, R.; Merz, K. M.; Pearlman, D. A.; Crowley, M.; Walker, R. C.; Zhang, W.; Wang, B.; Hayik, S.; Roitberg, A.; Seabra, G.; Wong, K. F.; Paesani, F.; Wu, X.; Brozell, S.; Tsui, V.; Gohlke, H.; Yang, L.; Tan, C.; Mongan, J.; Hornak, V.; Cui, G.; Beroza, P.; Mathews, D. H.; Schafmeister, C.; Ross, W. S.; Kollman, P. A.; University of California: San Francisco: (4) Bayly, C. I.; Cieplak, P.; Cornell, W.; Kollman, P. A. J. Phys. Chem. 1993, 97, (5 ) Cornell, W. D.; Cieplak, P.; Bayly, C. I.; Kollmann, P. A. J. Am. Chem. Soc. 1993, 115, (6) Frisch, M. J. T., G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. In Gaussian 03, Revision D.01; Gaussian, Inc.: Wallingford, CT: (7 ) Adams, J. E.; Cox, J. R.; Christiano, A. J.; Deakyne, C. A. J. Phys. Chem. A 2008, 112, (8) Breite, M. D.; Cox, J. R.; Adams, J. E. JACS 2010, 132, S15

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