Supporting Infromation

Supporting Infromation Aromatic Triazole Foldamers Induced by C H X (X = F, Cl) Intramolecular Hydrogen Bonding Jie Shang,, Nolan M. Gallagher, Fusheng Bie,, Qiaolian Li,, Yanke Che, Ying Wang,*,, and Hua Jiang,*,, # Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China # College of Chemistry, Beijing Normal University, Beijing 100875, China, Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304 University of Chinese Academy of Sciences, Beijing 100049, China. *To whom correspondence should be addressed. E-mail: hjiang@iccas.ac.cn and windsyn@iccas.ac.cn Contents 1. 1D and 2D NMR studies of compounds 1-4... 2 2. Crystal data of compounds 1 and 4... 12 3. Computational Details... 14 4 Variable temperature 1 H NMR experiment of 1, 2 and 4... 30 5. 1 H and 13 C NMR spectra of compounds 1-28... 33 1

1. 1D and 2D NMR studies of compounds 1-4 Figure S1. Partial 1 H NMR spectra (400 MHz, 298 K) of compound 1 in CDCl 3 (bottom) and DMSO-d 6 (top) at ambient temperature, [1] = 2 mm. Figure S2. Partial 1 H NMR spectra of compound 1 (400 MHz, 298 K) in CDCl 3 at different concentration, at ambient temperature. 2

Figure S3. Partial 1 H NMR spectra of compound 2 (400 MHz, 298 K) in CDCl 3 at different concentration, at ambient temperature. 3

Figure S4. Partial 1 H 1 H NOESY spectra (600 MHz, 298 K) of oligomer 1 in CDCl 3, [1]=8 mm. 1CO i 2 Bu ah 2 H 3 3' N 6 N 4 Hc 5 N 7 F 14 H H b ibuo 2 C 12 8 F F 13 11 9 H 10 d He 1 N N N H H H CO 2 i Bu 4

Figure S5 Partial 1 H 13 C HMBC spectra (600 MHz, 298 K) of oligomer 1 in CDCl 3, [1]=8 mm. Figure S6 Partial 1 H 13 C HSQC spectra (600 MHz, 298 K) of oligomer 1 in CDCl 3, [1]=8 mm. 5

1 CO i 2 Bu ah H 3 2 3' N 4 N N N N 5 N Hc 7 6 F i 14 13 8 H H b BuO 2 C 12 F F 10 9 11 H H H d e 15 16 F F NN N Hh N N N 21 22 17 20 H H fh 18 g 19 f CO CO i 2 Bu i 2 Bu 23 2 H H CO 2 i Bu Figure S7. Partial 1 H 13 C HMBC spectra (500 MHz, 298 K) of oligomer 2 in CDCl 3, [2]=14 mm. 6

Figure S8. Partial 1 H 13 C HSQC spectra (500 MHz, 298 K) of oligomer 2 in CDCl 3, [2]=14 mm. 7

Figure S9 Partial 1 H 1 H NOESY spectra (600 MHz, 298 K) of oligomer 3 in CDCl 3, [3]=10 mm.. 8

Figure S10 Partial 1 H 13 C HMBC spectra (600 MHz, 298 K) of oligomer 3 in CDCl 3, [3]=10 mm.. Figure S11 Partial 1 H 13 C HSQC spectra (600 MHz, 298 K) of oligomer 3 in CDCl 3, [3]=8 mm. 9

1 CO i 2 Bu 2 ah H 3 3' N 5 N N 6 4 N ch N 9 7 Cl N 11 8 H H b ibuo 2 C 10 Cl Cl 13 14 12 Hd N He H N O 15 4 H H O CO 2 i Bu Figure S12 Partial 1 H 13 C HMBC spectra (600 MHz, 298 K) of oligomer 4 in CDCl 3, [4]=8 mm.. 10

Figure S13 Partial 1 H 13 C HSQC spectra (600 MHz, 298 K) of oligomer 4 in CDCl 3, [4]=10 mm.. 11

2. Crystal data of compounds 1 and 4 Table S1. Crystal data and structure refinement for 1. Empirical formula C37 H37 F3 N6 O6 Formula weight 718.73 Temperature Wavelength Crystal system, space group 173(2) K 0.71073 A Monoclinic, P2(1)/c Unit cell dimensions a = 9.6484(19) A alpha = 90 deg. b = 13.075(3) A beta = 98.20(3) deg. c = 28.303(6) A gamma = 90 deg. Volume 3534.0(12) A^3 Z, Calculated density 4, 1.351 Mg/m^3 Absorption coefficient F(000) 1504 Crystal size Theta range for data collection Limiting indices 0.104 mm^-1 0.29 x 0.12 x 0.11 mm 2.13 to 25.00 deg. -11<=h<=11, -15<=k<=15, -33<=l<=31 Reflections collected / unique 21462 / 6214 [R(int) = 0.0840] Completeness to theta = 25.00 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.5763 Refinement method Data / restraints / parameters 6214 / 0 / 475 Goodness-of-fit on F^2 1.174 Full-matrix least-squares on F^2 Final R indices [I>2sigma(I)] R1 = 0.1041, wr2 = 0.1825 R indices (all data) R1 = 0.1483, wr2 = 0.2018 Largest diff. peak and hole 0.391 and -0.250 e.a^-3 12

Table S2. Crystal data and structure refinement for 4. Empirical formula C47 H55 Cl3 N8 O8 Formula weight 966.34 Temperature 173(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, C2/c Unit cell dimensions a = 47.727(9) A alpha = 90 deg. b = 14.350(3) A beta = 102.50(3) deg. c = 17.940(4) A gamma = 90 deg. Volume 11996(4) A^3 Z, Calculated density 8, 1.070 Mg/m^3 Absorption coefficient 0.202 mm^-1 F(000) 4064 Crystal size 0.21 x 0.13 x 0.05 mm Theta range for data collection 1.48 to 25.00 deg. Limiting indices -56<=h<=45, -15<=k<=17, -21<=l<=20 Reflections collected / unique 26859 / 10318 [R(int) = 0.1129] Completeness to theta = 25.00 97.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.2712 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 10318 / 0 / 607 Goodness-of-fit on F^2 1.352 Final R indices [I>2sigma(I)] R1 = 0.1162, wr2 = 0.2877 R indices (all data) R1 = 0.1604, wr2 = 0.3083 Largest diff. peak and hole 0.642 and -0.487 e.a^-3 13

3. Computational Details Figure S14 Ground state and higher-energy conformational minima of 1 4. Structure 1 (left): ground state (label: 1*, bottom) and unfolded minmum (label: 1-unfolded, top). Structure 2 (middle left): from top to bottom: ground state (label: 2*), oligomer with core region folded (label: 2-folded core), oligomer with the edges folded (label: 2-folded edges), and unfolded minima (label: 2-unfolded). Structure 3 (middle right): ground state (label: 3*, bottom) and unfolded minimum (label: 3-unfolded, top). Structure 4 (right): ground state (label: 4*, bottom) and unfolded minimum (label: 4-unfolded, top). The numbers nearby the arrow indicate the energy gap (kcal mol -1 ) between two different conformations. 14

3.a Computational Method and Results We utilized DFT to estimate the stability of the folded conformations of 1 4 by comparing the energy of the folded conformations with those of unfolded conformations. All calculations were carried out using the RB3LYP functional with the 6-31 G(d,p) basis set and 20 processing cores with 40 GB physical memory (Holland Computing Centre, University of Nebraska Lincoln). Frequencies were also calculated for every conformation to ensure that each stationary point represented a minimum on the potential energy surface (all conformation for 1 4 shown in Fig. S14 are minima by vibrational analysis). Structure 1 with folded conformation exhibits a nearly planar ground state (C 5 H F torsion angles are all less than 10 ), and short triazole proton/fluorine distances (2.3~2.4 Å), consistent with intramolecular C 5 H F hydrogen-bonding. On the other hand, the high-energy, unfolded conformation of 1 displays a nonplanar geometry (C 5 H F torsion angles are 54~58 ) and large triazole proton/fluorine distances (4.5~4.8 Å), showing a lack of C 5 H F hydrogen-bonding. The planar, folded geometry is ~ 12.1 kcal mol -1 lower in energy than the unfolded one. Thus, we estimate each C 5 H 2F planar interaction (i.e., one triazole proton being nearly coplanar with two neighboring fluorine atoms) to lower the energy by ~ 6 kcal mol -1. The ground state of structure 2 is nearly planar, with one end being twisted (C 5 H F torsion angles 13~27 ) to accommodate sterics. The triazole proton/fluorine distances are 2.3~2.5 Å, again indicative of C 5 H F hydrogen-bonding. The ground state of 2 posseses four favorable C 5 H 2F interactions. We examined two higher-energy conformations which possess only two C 5 H 2F interactions. The conformation which has a folded core but unfolded edges (Fig. S14, second from bottom) is nearly degenerate with the conformation which has folded edges but an unfolded core (Fig. S14, third from bottom). There is a small energetic preference (~ 1.3 kcal mol -1 ) for the folded-core conformation, which results perhaps because of the smaller steric inherence it possesses. Finally, the quasi-linear conformation of 2 (Fig S14 top) possesses no favorable C 5 H 2F interactions (C 5 H F torsion angles are 51~58, while C 5 H F distances are 4.4~4.9 Å). This conformation is ~ 26.3 kcal mol -1 higher in energy than the ground state, folded conformation. This is again consistent with each favorable C 5 H 2F interaction contributing 6 kcal mol -1 in stabilization energy. Compounds 3 and 4, which are similar to 1 except for the replacement of fluorine with chlorine, both possess non planar ground states. This is probably due to the increased size of the chlorine as well as increased C Cl bond length (relative to fluorine), which increases electrostatic repulsion and thus destabilizes a planar geometry. For 3, the ground state possesses C 5 H Cl torsion angles of 14~33 and C 5 H Cl distances of 2.7~2.9 Å, while the higher energy, unfolded conformation of 3 possess torsion C 5 H Cl torsion angles of 36~57 and C 5 H Cl distances of 2.9~4.9 Å. For 4, the ground state possesses C 5 H Cl torsion angles of 15~38 and C 5 H Cl distances of 2.7~3.0 Å, while the higher energy, unfolded conformation of 4 possesses C 5 H Cl torsion angles of 37 58 and C 5 H Cl distances of 3.0~4.9 Å. The energy difference between the ground and excited conformations of 3 and 4 is similar (4.8 5.5 kcal mol -1 ). Thus, we estimate each favorable C 5 H 2Cl interaction to lower the energy by ~ 3 kcal/mol. This is about half that of the C 5 H 2F interaction (~ 6 kcal mol -1 ), and can be rationalized in terms of the increased electrostatic repulsion of chlorine atoms (versus fluorine atoms) in a folded state, which leads to less folding and less favorable hydrogen bonding as evidenced by the geometries of the ground states of 3 and 4. These results are summarized in Table S3. 15

Table S3. Important geometrical parameters and energies of various conformations of 1-4 Structure C 5 H X torsion angle C 5 H X distance (Å) Energy (Hartree) 1* <10 2.3-2.4-2157.7886469 1-unfolded 54-58 4.5-4.8-2157.7694277 2* 1-27 2.3-2.5-3756.205624 2-folded core 2-folded edges 2-22 (folded region) 52-58 (unfolded region) 2.3-2.4 (folded region) 4.5-4.9 (unfolded region) 3-18 (folded region) 2.3-2.4 (folded region) 55-58 (unfolded region) 4.5-4.9 (unfolded region) -3756.185257-3756.1873624 2-unfolded 51-58 4.4-4.9-3756.1638015 3* 14-33 2.7-2.9-3647.8169205 3-unfolded 36-57 2.9-4.9-3647.8080872 4* 15-38 2.7-3.0-3654.8973705 4-unfolded 37-58 3.0-4.9-3654.8896813 *= ground state conformation; 1 Hartree = 627.5 kcal mol -1. 6.b Optimized geometries/coordinate of ground state and higher-energy conformational minima of 1-4 obtained from Gaussian. (Fig S14). 1* (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-1.245754 2.090607-0.145316 2 6 0-0.019476 1.419082-0.177839 3 6 0 1.223495 2.057799-0.145428 4 6 0 1.222000 3.457857-0.073277 5 6 0 0.017911 4.166327-0.037576 6 6 0-1.203817 3.488871-0.073328 7 1 0 2.169960 3.978924-0.045505 8 1 0-2.129564 4.050581-0.044800 9 6 0 2.488620 1.318147-0.180259 10 6 0-2.529469 1.383823-0.179599 11 9 0-0.036827 0.059984-0.245030 12 7 0-4.710659 1.255650-0.179541 13 7 0-4.193368-0.009811-0.246852 14 7 0 4.117014-0.117176-0.246389 15 7 0 4.666278 1.134482-0.185118 16 6 0 2.756466-0.034853-0.246004 17 1 0 2.121414-0.898562-0.290772 18 7 0 3.691712 1.982578-0.146546 19 6 0-2.831326 0.038163-0.249620 20 1 0-2.218562-0.841266-0.299406 21 7 0-3.715177 2.078453-0.140433 22 6 0 4.966925-1.250588-0.265073 23 6 0 4.548265-2.475458-0.799902 24 6 0 6.263385-1.159183 0.244250 25 6 0 5.380151-3.586647-0.824987 16

26 6 0 7.115201-2.266431 0.214232 27 1 0 6.613817-0.222529 0.658886 28 6 0 6.671489-3.484437-0.318625 29 1 0 5.001073-4.509608-1.249038 30 1 0 7.334070-4.340736-0.332274 31 9 0 3.303044-2.592035-1.306011 32 6 0-5.071656-1.121146-0.267530 33 6 0-6.362996-1.000009 0.248677 34 6 0-4.686698-2.352954-0.811568 35 6 0-7.242639-2.085279 0.216284 36 6 0-5.546427-3.442636-0.839185 37 6 0-6.832376-3.310847-0.325981 38 1 0-5.192868-4.372302-1.270580 39 1 0-7.516510-4.150000-0.341517 40 1 0-6.687511-0.057109 0.670282 41 9 0-3.447130-2.497894-1.324416 42 6 0-0.021091 5.656386 0.041259 43 8 0-1.040778 6.315617 0.075676 44 8 0 1.215520 6.201195 0.071201 45 6 0 1.251057 7.634833 0.148582 46 1 0 0.753973 7.983021 1.057248 47 1 0 2.307482 7.901318 0.162517 48 1 0 0.753102 8.078893-0.716769 49 6 0-8.605459-1.880528 0.789566 50 8 0-8.992205-0.840703 1.282176 51 8 0-9.369007-2.992115 0.700296 52 6 0 8.485530-2.092405 0.779772 53 8 0 8.901080-1.058745 1.261983 54 8 0 9.219684-3.223904 0.696498 55 6 0-10.697731-2.864571 1.235010 56 1 0-11.167253-3.836707 1.088134 57 1 0-10.660468-2.610607 2.296857 58 1 0-11.250585-2.085528 0.705015 59 6 0 10.553589-3.126673 1.224749 60 1 0 10.527474-2.861231 2.284099 61 1 0 10.996294-4.112445 1.085820 62 1 0 11.124880-2.368082 0.684723 1-unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 1.154485 0.277920-0.099598 2 6 0-0.096646-0.326156-0.300479 3 6 0-1.256244 0.410729-0.590791 4 6 0-1.134158 1.800931-0.679479 5 6 0 0.095136 2.435644-0.483849 6 6 0 1.229910 1.672332-0.195344 7 1 0-1.996706 2.412193-0.920457 8 1 0 2.177399 2.168832-0.024045 9 6 0-2.560883-0.236976-0.786258 10 6 0-3.810472 0.248732-0.458765 11 7 0-2.728196-1.459948-1.391421 12 1 0-4.140003 1.156286 0.020853 13 6 0 2.358513-0.513491 0.190305 14 6 0-6.085495-0.746257-0.753550 15 6 0-6.898192-1.091377-1.842972 16 6 0-6.688256-0.433200 0.461957 17 6 0-8.282253-1.137655-1.721493 18 6 0-8.080879-0.456652 0.591179 19 1 0-6.084665-0.178554 1.325957 20 6 0-8.876115-0.817832-0.504231 21 1 0-9.953739-0.845405-0.399108 22 9 0-0.186084-1.654738-0.211742 17

23 7 0 4.381619-1.281163 0.336915 24 7 0 3.572063-2.097234 1.079588 25 7 0-3.988252-1.748387-1.456659 26 7 0-4.674828-0.707894-0.891672 27 9 0-6.340576-1.363305-3.026070 28 7 0 2.366579-1.636014 0.984096 29 6 0 3.652966-0.279637-0.226389 30 1 0 4.087895 0.457094-0.882330 31 6 0 5.781407-1.492849 0.269551 32 6 0 6.300432-2.771509 0.018222 33 6 0 6.666113-0.431018 0.439814 34 6 0 7.671834-2.990211-0.047956 35 6 0 8.047210-0.634807 0.355013 36 1 0 6.295011 0.565513 0.651241 37 6 0 8.547831-1.921710 0.117893 38 1 0 8.027606-3.995667-0.242416 39 1 0 9.617904-2.080056 0.063104 40 9 0 5.469691-3.797688-0.180684 41 6 0 0.134505 3.919539-0.592033 42 8 0-0.834571 4.618653-0.816651 43 8 0 1.379676 4.417935-0.412508 44 6 0 8.927673 0.553429 0.539227 45 8 0 8.520189 1.682979 0.727428 46 8 0 10.238294 0.236340 0.471864 47 6 0 1.483901 5.848061-0.498602 48 1 0 2.536185 6.076340-0.331202 49 1 0 1.166233 6.197923-1.483768 50 1 0 0.861457 6.325508 0.261943 51 6 0 11.145598 1.338823 0.642438 52 1 0 12.144344 0.910846 0.563551 53 1 0 10.985944 2.090261-0.134354 54 1 0 11.002021 1.804863 1.619958 55 1 0-8.870692-1.411708-2.589804 56 6 0-8.652174-0.101192 1.921178 57 8 0-7.988313 0.234279 2.882069 58 8 0-9.999389-0.191796 1.941855 59 6 0-10.615836 0.137485 3.198645 60 1 0-11.686413 0.010136 3.041873 61 1 0-10.259337-0.530353 3.986196 62 1 0-10.387183 1.168299 3.479082 2* (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-5.629445 1.477125 0.472249 2 6 0-5.052025 0.232553 0.203560 3 6 0-5.755959-0.975130 0.202875 4 6 0-7.127706-0.915850 0.484403 5 6 0-7.743296 0.308518 0.760481 6 6 0-7.000855 1.492854 0.756755 7 1 0-7.700179-1.834262 0.485256 8 1 0-7.491647 2.433575 0.975129 9 6 0-5.103555-2.257085-0.078678 10 6 0-4.849022 2.717987 0.462319 11 9 0-3.719373 0.194715-0.072975 12 7 0-4.532621 4.855779 0.776865 13 7 0-3.382087 4.309188 0.274012 14 7 0-3.767013-3.918089-0.482239 15 7 0-5.039718-4.415182-0.427703 16 6 0-3.773950-2.573618-0.270806 17 1 0-2.879167-1.980637-0.271044 18 7 0-5.830043-3.419656-0.183936 19 6 0-3.550221 2.972430 0.068906 18

20 1 0-2.778074 2.341085-0.325203 21 7 0-5.399916 3.903875 0.884696 22 6 0-2.677135-4.773558-0.777980 23 6 0-1.424190-4.554272-0.198685 24 6 0-2.836289-5.847517-1.650760 25 6 0-0.310487-5.347180-0.486799 26 6 0-1.742944-6.669394-1.942739 27 1 0-3.800749-6.045069-2.101503 28 6 0-0.491107-6.415546-1.376551 29 1 0 0.358532-7.039673-1.620966 30 9 0-1.282000-3.518773 0.662317 31 6 0-2.270757 5.151563 0.013824 32 6 0-2.465340 6.523927-0.143683 33 6 0-0.969689 4.645366-0.078382 34 6 0-1.370821 7.358517-0.383733 35 6 0 0.140773 5.454780-0.337231 36 6 0-0.081934 6.831228-0.484017 37 1 0 0.764094 7.476376-0.680678 38 1 0-3.461252 6.941401-0.073861 39 9 0-0.772948 3.312912 0.084636 40 6 0-9.201009 0.409068 1.066465 41 8 0-9.782027 1.448645 1.305368 42 8 0-9.813028-0.795821 1.049132 43 6 0-11.220683-0.771418 1.333338 44 1 0-11.750618-0.161687 0.597566 45 1 0-11.548344-1.809182 1.279659 46 1 0-11.404490-0.360214 2.328883 47 6 0-1.647829 8.818529-0.543297 48 8 0-2.755616 9.312202-0.485717 49 8 0-0.523050 9.531137-0.760161 50 6 0-1.971889-7.801212-2.891344 51 8 0-3.038389-8.040897-3.419911 52 8 0-0.855398-8.529670-3.096574 53 6 0-0.715425 10.946405-0.924397 54 1 0 0.279412 11.359472-1.086939 55 1 0-1.361907 11.147889-1.781744 56 1 0-1.170864 11.377062-0.029609 57 6 0-1.002479-9.635935-4.003559 58 1 0-1.314149-9.283387-4.989462 59 1 0-0.020207-10.104090-4.054838 60 1 0-1.747454-10.341452-3.628457 61 6 0 1.496750 4.909456-0.451604 62 6 0 1.973142 3.613580-0.408103 63 7 0 2.568977 5.745012-0.651148 64 1 0 1.488655 2.665840-0.271697 65 6 0 1.004048-5.067460 0.097510 66 6 0 1.373955-4.269162 1.162071 67 7 0 2.143223-5.634688-0.420316 68 1 0 0.812183-3.658229 1.845103 69 7 0 2.726392-4.394770 1.227865 70 7 0 3.177282-5.234676 0.246568 71 7 0 3.657433 5.052855-0.732420 72 7 0 3.318034 3.735754-0.587795 73 6 0 4.329545 2.743940-0.668443 74 6 0 5.527897 3.022194-1.327802 75 6 0 4.171188 1.480835-0.084710 76 6 0 6.540928 2.061171-1.390126 77 1 0 5.678353 3.991050-1.786767 78 6 0 5.163763 0.513618-0.151021 79 6 0 6.358954 0.801736-0.802209 80 1 0 4.992569-0.450932 0.311416 81 1 0 7.136616 0.049688-0.848799 82 6 0 3.648780-3.766692 2.100763 83 6 0 3.357828-3.604832 3.460491 84 6 0 4.874291-3.312406 1.617961 85 6 0 4.260378-3.011739 4.333263 86 6 0 5.793770-2.713676 2.485589 87 1 0 5.116286-3.427178 0.568343 88 6 0 5.487172-2.570580 3.846013 19

89 1 0 3.988435-2.910148 5.377720 90 1 0 6.202478-2.104127 4.512170 91 9 0 3.023555 1.185185 0.564073 92 9 0 2.171955-4.029486 3.931175 93 6 0 7.792446 2.435481-2.112532 94 8 0 7.972511 3.503422-2.661677 95 8 0 8.711958 1.446151-2.088005 96 6 0 7.063489-2.200249 1.894893 97 8 0 7.272161-2.120413 0.698217 98 8 0 7.949816-1.819475 2.833479 99 6 0 9.938361 1.735213-2.780498 100 1 0 10.554935 0.843975-2.668511 101 1 0 9.743411 1.938165-3.836071 102 1 0 10.431831 2.604635-2.339750 103 6 0 9.190258-1.284329 2.334794 104 1 0 9.007634-0.379915 1.749858 105 1 0 9.785214-1.056663 3.218179 106 1 0 9.696599-2.019803 1.706228 2-folded core: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-0.126785 5.814482-0.014601 2 6 0-1.197695 4.930371-0.181578 3 6 0-2.491259 5.327590-0.532999 4 6 0-2.709594 6.698451-0.728368 5 6 0-1.666263 7.614420-0.568526 6 6 0-0.387668 7.176138-0.213648 7 1 0-3.700888 7.033455-1.003957 8 1 0 0.411838 7.896763-0.092191 9 6 0-3.590172 4.371622-0.698213 10 6 0 1.217672 5.359466 0.351570 11 9 0-0.966681 3.603873 0.008559 12 7 0 3.321952 5.641830 0.868412 13 7 0 3.044887 4.300968 0.853178 14 7 0-4.937702 2.672965-0.808554 15 7 0-5.641279 3.788515-1.175005 16 6 0-3.651396 3.005667-0.505088 17 1 0-2.921790 2.285373-0.187823 18 7 0-4.833145 4.794638-1.105480 19 6 0 1.736903 4.092794 0.533621 20 1 0 1.303552 3.113184 0.461301 21 7 0 2.230225 6.264040 0.567840 22 6 0-5.585306 1.412030-0.824008 23 6 0-5.169087 0.373146 0.018254 24 6 0-6.667122 1.202805-1.678311 25 6 0-5.806494-0.875026 0.031663 26 6 0-7.322780-0.030173-1.678912 27 1 0-7.004307 1.997494-2.331086 28 6 0-6.896073-1.054678-0.829719 29 1 0-7.429246-1.997220-0.826511 30 9 0-4.113018 0.580680 0.820043 31 6 0 4.069871 3.377224 1.174183 32 6 0 5.109783 3.762708 2.018769 33 6 0 4.077642 2.089767 0.623370 34 6 0 6.140777 2.864708 2.303924 35 6 0 5.087583 1.162983 0.913070 36 6 0 6.121468 1.576244 1.762796 37 1 0 6.908349 0.879278 2.023432 38 1 0 5.121071 4.756824 2.446823 39 9 0 3.092202 1.747702-0.221361 40 6 0-1.863590 9.080152-0.766500 41 8 0-0.989229 9.914582-0.643342 20

42 8 0-3.137110 9.386450-1.102407 43 6 0-3.395996 10.783524-1.307825 44 1 0-2.774522 11.175053-2.116905 45 1 0-4.452030 10.850819-1.567899 46 1 0-3.186702 11.351293-0.397902 47 6 0 7.224978 3.327972 3.218447 48 8 0 7.258817 4.422971 3.740742 49 8 0 8.177671 2.385774 3.402465 50 6 0-8.476801-0.196621-2.609939 51 8 0-8.870921 0.661655-3.372334 52 8 0-9.041333-1.421836-2.512977 53 6 0 9.252926 2.769169 4.276725 54 1 0 9.922277 1.910145 4.312531 55 1 0 9.771884 3.646295 3.883376 56 1 0 8.871912 3.002295 5.273698 57 6 0-10.165389-1.645145-3.381222 58 1 0-9.868136-1.542408-4.427481 59 1 0-10.498412-2.661744-3.174251 60 1 0-10.961673-0.928110-3.168717 61 6 0 5.089659-0.184113 0.327946 62 6 0-5.355784-1.964882 0.907222 63 7 0-4.535193-2.911449 2.695810 64 7 0 5.629919-2.127897-0.464856 65 7 0 4.264317-2.063234-0.418080 66 6 0 6.174312-0.967816-0.010915 67 1 0 7.238866-0.803771 0.032646 68 7 0 3.948895-0.901241 0.057099 69 6 0 6.295319-3.262409-0.996989 70 6 0 7.312832-3.112024-1.935382 71 6 0 5.944480-4.553842-0.578485 72 6 0 7.978374-4.231157-2.446027 73 1 0 7.594326-2.127056-2.290933 74 6 0 6.584849-5.674811-1.093911 75 6 0 7.604871-5.514844-2.027228 76 1 0 6.279759-6.654223-0.743234 77 1 0 8.114240-6.380756-2.432093 78 9 0 4.992691-4.715408 0.344825 79 6 0 9.063032-3.987817-3.439838 80 8 0 9.418128-2.884203-3.803796 81 8 0 9.611535-5.135029-3.891418 82 6 0 10.666303-4.972790-4.856254 83 1 0 10.989118-5.982020-5.109159 84 1 0 10.296517-4.452563-5.742716 85 1 0 11.491773-4.399629-4.428021 86 7 0-4.795583-1.768752 2.146893 87 6 0-5.437366-3.325685 0.688895 88 1 0-5.802006-3.914965-0.136877 89 7 0-4.926268-3.884732 1.817734 90 6 0-4.721040-5.259086 2.104150 91 6 0-5.099962-5.790598 3.345261 92 6 0-4.149810-6.103620 1.156014 93 6 0-4.900068-7.133682 3.642749 94 6 0-3.962870-7.461150 1.436195 95 1 0-3.832197-5.717670 0.193769 96 6 0-4.332781-7.971625 2.687349 97 1 0-5.205762-7.500992 4.615838 98 1 0-4.176885-9.020936 2.905791 99 9 0-5.680638-5.002805 4.254097 100 6 0-3.356365-8.304795 0.367177 101 8 0-3.054304-7.895044-0.736169 102 8 0-3.181061-9.583873 0.761427 103 6 0-2.599110-10.454941-0.224068 104 1 0-1.608727-10.096531-0.513831 105 1 0-2.530273-11.431870 0.253102 106 1 0-3.231671-10.503937-1.113391 21

2-folded edges: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-1.283805-3.161089-0.229739 2 6 0-0.169372-2.420350 0.194656 3 6 0 1.151181-2.829151-0.051609 4 6 0 1.338737-4.024287-0.752724 5 6 0 0.252700-4.787219-1.189740 6 6 0-1.049284-4.352958-0.925544 7 1 0 2.339086-4.372856-0.983996 8 1 0-1.888978-4.957234-1.247165 9 6 0 2.305956-2.049641 0.416255 10 6 0 3.530493-2.517976 0.847334 11 7 0 2.341550-0.676077 0.454709 12 1 0 3.930546-3.510932 0.974705 13 6 0-2.657942-2.708690 0.028895 14 6 0 5.559270-1.304648 1.659214 15 6 0 6.497465-0.438488 1.086172 16 6 0 5.930673-2.080448 2.752755 17 6 0 7.796377-0.310886 1.590786 18 6 0 7.230997-1.990452 3.261037 19 1 0 5.220067-2.747637 3.226885 20 6 0 8.149668-1.108410 2.689850 21 1 0 9.152807-1.026963 3.087876 22 9 0-0.373889-1.281456 0.860090 23 7 0-4.783767-2.290000-0.066240 24 7 0-4.321066-1.822100 1.133275 25 7 0 3.499585-0.279040 0.875896 26 7 0 4.250309-1.397001 1.119813 27 9 0 6.142624 0.279943 0.008033 28 7 0-3.051707-2.071343 1.181510 29 6 0-3.769694-2.853949-0.776032 30 1 0-3.908377-3.255269-1.766955 31 6 0-6.156548-2.205553-0.412910 32 6 0-6.843759-0.993526-0.278938 33 6 0-6.832658-3.318806-0.901568 34 6 0-8.199146-0.868096-0.603835 35 6 0-8.182449-3.214953-1.254504 36 1 0-6.329504-4.273658-1.000660 37 6 0-8.858606-2.003666-1.098375 38 1 0-9.905682-1.921367-1.359731 39 9 0-6.175079 0.085177 0.159026 40 6 0 0.543493-6.048873-1.924159 41 8 0 1.661455-6.466447-2.156881 42 8 0-0.581599-6.692469-2.311785 43 6 0-8.846799-4.443713-1.779788 44 8 0-8.277362-5.504422-1.949163 45 8 0-10.152845-4.247015-2.047857 46 6 0-0.368555-7.924167-3.019942 47 1 0-1.362769-8.304914-3.252214 48 1 0 0.199780-7.747345-3.936192 49 1 0 0.179627-8.635367-2.397431 50 6 0-10.856825-5.392378-2.557320 51 1 0-11.884056-5.061505-2.705284 52 1 0-10.418127-5.722441-3.501948 53 1 0-10.815774-6.216154-1.841027 54 6 0 7.569694-2.856409 4.428613 55 8 0 6.796608-3.644711 4.936725 56 8 0 8.833730-2.668729 4.857424 57 6 0 9.228731-3.474239 5.980947 58 1 0 10.262890-3.200800 6.186773 59 1 0 8.594435-3.262855 6.844960 60 1 0 9.151506-4.536265 5.736613 61 6 0-8.915900 0.400734-0.456552 62 6 0-8.506581 1.630259 0.021778 63 7 0-10.235234 0.508452-0.824138 64 1 0-7.569103 1.983185 0.407922 22

65 6 0 8.773717 0.602322 0.993844 66 6 0 8.663479 1.507717-0.043443 67 7 0 10.059633 0.664013 1.473407 68 1 0 7.846054 1.781109-0.683497 69 7 0-9.610028 2.420901-0.081137 70 7 0-10.656530 1.710385-0.603434 71 6 0-9.801116 3.777760 0.283555 72 6 0-8.734031 4.684189 0.316850 73 6 0-11.078098 4.241709 0.601188 74 6 0-8.916940 6.016064 0.663227 75 6 0-11.278095 5.582781 0.939065 76 6 0-10.194389 6.470964 0.973039 77 1 0-10.355272 7.507177 1.243023 78 7 0 10.737182 1.538008 0.804474 79 7 0 9.899137 2.072272-0.136433 80 6 0 10.395911 3.047972-1.037263 81 6 0 9.549418 3.985704-1.641672 82 6 0 11.760477 3.102210-1.323891 83 6 0 10.032685 4.950744-2.514952 84 6 0 12.261729 4.076205-2.191455 85 6 0 11.395213 5.000885-2.790262 86 1 0 11.789180 5.749037-3.466752 87 1 0-8.054516 6.672826 0.675881 88 1 0-11.920235 3.561685 0.578908 89 9 0-7.492191 4.261609 0.007046 90 6 0-12.670861 6.006665 1.268279 91 8 0-13.630650 5.263245 1.268424 92 8 0-12.746081 7.321513 1.569486 93 6 0-14.062071 7.799126 1.898270 94 1 0-14.451638 7.275116 2.774105 95 1 0-13.944294 8.861941 2.106878 96 1 0-14.745851 7.643855 1.060611 97 1 0 12.436393 2.391190-0.865947 98 1 0 9.331461 5.649982-2.956150 99 9 0 8.228400 3.957998-1.376330 100 6 0 13.731426 4.071396-2.451768 101 8 0 14.509593 3.274628-1.968537 102 8 0 14.103746 5.060422-3.293528 103 6 0 15.509986 5.114221-3.589407 104 1 0 15.837996 4.184600-4.060214 105 1 0 15.633893 5.955129-4.270944 106 1 0 16.087756 5.270237-2.675492 2-unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-1.346233-2.690893-0.235963 2 6 0-0.206466-1.971143 0.156032 3 6 0 1.080267-2.271942-0.319458 4 6 0 1.205039-3.335068-1.219400 5 6 0 0.092485-4.074345-1.629240 6 6 0-1.174304-3.748630-1.136254 7 1 0 2.174699-3.593609-1.629981 8 1 0-2.032739-4.335422-1.440136 9 6 0 2.265830-1.516390 0.108285 10 6 0 3.555290-1.979089 0.273756 11 7 0 2.264040-0.167264 0.373247 12 1 0 4.001307-2.955310 0.171885 13 6 0-2.686320-2.350891 0.262945 14 6 0 5.646218-0.800832 0.970903 15 6 0 6.463628 0.173013 0.379543 16 6 0 6.194877-1.705302 1.874206 17 6 0 7.826857 0.274367 0.696627 18 6 0 7.556071-1.640233 2.185886 23

19 1 0 5.575216-2.454794 2.353054 20 6 0 8.354235-0.649423 1.609062 21 1 0 9.399157-0.584291 1.887107 22 9 0-0.353977-0.960632 1.014648 23 7 0-4.816281-2.018443 0.499242 24 7 0-4.218717-1.758564 1.702779 25 7 0 3.458936 0.220849 0.683382 26 7 0 4.272548-0.878118 0.624722 27 9 0 5.933008 0.988547-0.528144 28 7 0-2.948372-1.954555 1.553280 29 6 0-3.884882-2.396286-0.418267 30 1 0-4.134246-2.613231-1.444383 31 6 0-6.222884-1.943537 0.336513 32 6 0-6.925130-0.812134 0.777058 33 6 0-6.910253-2.978642-0.289535 34 6 0-8.316171-0.709267 0.622343 35 6 0-8.292002-2.886265-0.478775 36 1 0-6.387648-3.867850-0.622724 37 6 0-8.983298-1.765021-0.012748 38 1 0-10.059232-1.719946-0.129844 39 9 0-6.245483 0.195756 1.316678 40 6 0 0.316374-5.192381-2.585252 41 8 0 1.403896-5.519610-3.019793 42 8 0-0.833981-5.818367-2.927283 43 6 0-8.970957-4.025268-1.158455 44 8 0-8.395734-5.008814-1.580975 45 8 0-10.305931-3.843828-1.259163 46 6 0-0.684160-6.914356-3.843220 47 1 0-1.689686-7.302595-4.003583 48 1 0-0.249470-6.571712-4.785373 49 1 0-0.037706-7.685699-3.417756 50 6 0-11.022076-4.912000-1.902390 51 1 0-12.068832-4.609939-1.893411 52 1 0-10.668905-5.047612-2.927301 53 1 0-10.886555-5.847668-1.355178 54 6 0 8.088653-2.636277 3.158373 55 8 0 7.421729-3.512698 3.671242 56 8 0 9.404996-2.460530 3.406595 57 6 0 9.979980-3.386702 4.344514 58 1 0 11.029840-3.107145 4.425952 59 1 0 9.483754-3.306323 5.314374 60 1 0 9.880642-4.411978 3.980618 61 6 0-9.053373 0.479404 1.070420 62 6 0 8.693238 1.279895 0.068813 63 7 0-9.573264 2.165523 2.355565 64 7 0-10.474428 2.095598 1.327576 65 7 0 10.354479 2.385233-0.778720 66 7 0 9.255332 3.200588-0.803829 67 6 0-10.173064 1.056060 0.505184 68 1 0-10.753192 0.823300-0.373164 69 7 0-8.729406 1.198093 2.196094 70 6 0-11.499361 3.065588 1.181116 71 6 0-12.312791 3.409968 2.270051 72 6 0-11.718563 3.685948-0.045794 73 6 0-13.315661 4.364366 2.144001 74 6 0-12.737683 4.632965-0.190233 75 1 0-11.094434 3.452272-0.901101 76 6 0-13.530721 4.976203 0.912575 77 1 0-13.918685 4.601736 3.013078 78 1 0-14.312066 5.718087 0.801680 79 9 0-12.138291 2.800594 3.445556 80 6 0-12.916344 5.245867-1.537432 81 8 0-12.261590 4.943887-2.515695 82 8 0-13.892817 6.177323-1.552062 83 6 0-14.116432 6.811749-2.823524 84 1 0-14.401684 6.072364-3.575409 85 1 0-14.924593 7.523091-2.657367 86 1 0-13.212707 7.326101-3.158077 87 6 0 10.036413 1.180335-0.235309 24

88 1 0 10.748471 0.375035-0.153683 89 7 0 8.267655 2.533268-0.301114 90 6 0 11.619889 2.839491-1.229870 91 6 0 11.743230 3.495756-2.463226 92 6 0 12.762082 2.631265-0.461377 93 6 0 12.977293 3.948641-2.915455 94 6 0 14.012233 3.063813-0.915419 95 1 0 12.694847 2.141478 0.503641 96 6 0 14.114385 3.731201-2.143129 97 1 0 13.025412 4.453264-3.873754 98 1 0 15.081771 4.075304-2.487930 99 9 0 10.664621 3.674758-3.229553 100 6 0 15.189338 2.794488-0.041367 101 8 0 15.131149 2.199896 1.017044 102 8 0 16.335344 3.284284-0.559286 103 6 0 17.513297 3.059327 0.234793 104 1 0 17.682763 1.989094 0.373552 105 1 0 18.333097 3.509308-0.323967 106 1 0 17.409897 3.531275 1.214537 3* (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-1.165785 2.402488-0.013315 2 6 0 0.027307 1.657460-0.113901 3 6 0 1.289291 2.271900-0.243497 4 6 0 1.332288 3.674480-0.276483 5 6 0 0.169253 4.433801-0.171395 6 6 0-1.064312 3.800377-0.037500 7 1 0 2.293287 4.158082-0.389938 8 1 0-1.963186 4.398021 0.050226 9 6 0 2.579669 1.568243-0.359145 10 6 0-2.519358 1.836826 0.131003 11 7 0-4.634487 1.968318 0.687447 12 7 0-4.397665 0.743260 0.119026 13 7 0 4.335501 0.286418-0.315392 14 7 0 4.712785 1.487196-0.858560 15 6 0 3.013267 0.310144 0.010274 16 1 0 2.522702-0.522289 0.479408 17 7 0 3.665341 2.238420-0.882577 18 6 0-3.086319 0.630104-0.229559 19 1 0-2.687825-0.254915-0.689629 20 7 0-3.517312 2.612373 0.680367 21 6 0 5.318799-0.711652-0.096491 22 6 0 5.119813-2.055795-0.469662 23 6 0 6.528596-0.309446 0.470363 24 6 0 6.162543-2.964906-0.227958 25 6 0 7.562930-1.223845 0.666729 26 1 0 6.669926 0.728080 0.747643 27 6 0 7.377857-2.559637 0.311849 28 1 0 8.162413-3.291203 0.451530 29 6 0-5.448697-0.210066 0.077092 30 6 0-6.178587-0.414257 1.247821 31 6 0-5.785673-0.903178-1.103020 32 6 0-7.229187-1.331031 1.282088 33 6 0-6.837269-1.831822-1.039814 34 6 0-7.542875-2.060582 0.136411 35 1 0-8.330401-2.802232 0.142309 36 1 0-5.923193 0.142902 2.141029 37 6 0 0.185817 5.927509-0.200283 38 8 0-0.807884 6.622702-0.139780 39 8 0 1.437390 6.423442-0.301338 40 6 0 1.527216 7.857302-0.339173 41 1 0 1.109671 8.291416 0.572370 25

42 1 0 2.590158 8.081823-0.420593 43 1 0 0.982657 8.252895-1.199765 44 6 0-7.960318-1.511466 2.574553 45 8 0-7.675798-0.923773 3.596810 46 8 0-8.965091-2.400025 2.465827 47 6 0 8.835437-0.721504 1.271851 48 8 0 9.010916 0.430005 1.610510 49 8 0 9.754904-1.696121 1.395011 50 6 0-9.717924-2.631202 3.672255 51 1 0-10.478257-3.363550 3.404983 52 1 0-9.066320-3.018840 4.458354 53 1 0-10.178175-1.702393 4.015959 54 6 0 11.012740-1.289381 1.967982 55 1 0 10.861558-0.897960 2.976297 56 1 0 11.626689-2.188498 1.990316 57 1 0 11.478415-0.517453 1.351640 58 17 0 3.672150-2.525657-1.302928 59 17 0-4.889673-0.624492-2.562122 60 17 0-0.064537-0.103303-0.074273 61 7 0 6.036570-4.407042-0.525764 62 8 0 7.042026-4.966509-0.957529 63 8 0 4.964862-4.950352-0.283949 64 7 0-7.278842-2.611489-2.215513 65 8 0-7.605326-3.777567-2.002308 66 8 0-7.326928-2.043374-3.299672 3-unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 1.211757 0.907903 0.189114 2 6 0-0.024834 0.261541-0.010128 3 6 0-1.196583 0.998624-0.279254 4 6 0-1.107002 2.393027-0.337426 5 6 0 0.107710 3.052622-0.146576 6 6 0 1.257647 2.305045 0.111866 7 1 0-1.990221 2.983257-0.554799 8 1 0 2.200259 2.812218 0.278299 9 6 0-2.514684 0.373221-0.499460 10 6 0-3.710866 0.690671 0.104808 11 7 0-2.754366-0.611831-1.427924 12 1 0-3.960694 1.382260 0.891821 13 6 0 2.465104 0.182832 0.475740 14 6 0-6.003301-0.320178-0.220738 15 6 0-6.907622 0.755726-0.119460 16 6 0-6.457066-1.634597-0.100309 17 6 0-8.257390 0.458351 0.128366 18 6 0-7.808691-1.905704 0.109682 19 1 0-5.751918-2.452479-0.185262 20 6 0-8.714288-0.851144 0.221252 21 1 0-9.768473-1.031772 0.383282 22 7 0 4.507264-0.542252 0.508664 23 7 0 3.840890-1.128791 1.551953 24 7 0-4.008193-0.919561-1.425544 25 7 0-4.625600-0.124708-0.489536 26 7 0 2.623868-0.693337 1.522748 27 6 0 3.675171 0.291383-0.174302 28 1 0 3.987574 0.840185-1.048445 29 6 0 5.893338-0.768940 0.300097 30 6 0 6.372637-2.053903-0.030327 31 6 0 6.768938 0.305961 0.421910 32 6 0 7.756561-2.201534-0.218490 33 6 0 8.137593 0.140758 0.200686 34 1 0 6.391585 1.285196 0.694199 26

35 6 0 8.629340-1.121894-0.125359 36 1 0 9.683435-1.281546-0.309348 37 6 0 0.114931 4.540942-0.226588 38 8 0-0.874030 5.220034-0.419327 39 8 0 1.351991 5.058972-0.060744 40 6 0 9.016761 1.342277 0.330575 41 8 0 8.601199 2.454552 0.584027 42 8 0 10.313159 1.045505 0.131891 43 6 0 1.427985 6.493499-0.120371 44 1 0 2.479142 6.737763 0.029478 45 1 0 1.082630 6.855444-1.091570 46 1 0 0.813001 6.942824 0.662826 47 6 0 11.225711 2.155556 0.236672 48 1 0 12.213767 1.738611 0.047857 49 1 0 10.980114 2.920201-0.503416 50 1 0 11.175040 2.595330 1.235023 51 6 0-8.227419-3.337516 0.221403 52 8 0-7.458049-4.272321 0.149328 53 8 0-9.554176-3.461334 0.411637 54 17 0 5.255323-3.344762-0.292427 55 17 0-0.105875-1.478101 0.079418 56 17 0-6.370176 2.380974-0.408155 57 7 0 8.377349-3.506037-0.532457 58 8 0 9.325379-3.483896-1.315758 59 8 0 7.938815-4.501091 0.030373 60 7 0-9.276400 1.512717 0.311723 61 8 0-10.387372 1.289068-0.164112 62 8 0-8.962234 2.506983 0.955909 63 6 0-10.037536-4.813696 0.524484 64 1 0-11.112964-4.727051 0.672442 65 1 0-9.815918-5.373281-0.386834 66 1 0-9.568569-5.315213 1.373823 4* (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0-1.148534 2.678734-0.035595 2 6 0 0.050553 1.942506-0.130816 3 6 0 1.301249 2.560025-0.334033 4 6 0 1.326171 3.958689-0.449089 5 6 0 0.157402 4.710707-0.353247 6 6 0-1.064073 4.073870-0.144780 7 1 0 2.278140 4.443675-0.618825 8 1 0-1.967483 4.665510-0.063733 9 6 0 2.596078 1.864397-0.448512 10 6 0-2.490426 2.109380 0.183832 11 7 0-4.591493 2.250987 0.790406 12 7 0-4.354932 0.998290 0.294641 13 7 0 4.368685 0.607979-0.377967 14 7 0 4.712483 1.769860-1.011930 15 6 0 3.059295 0.638521-0.010280 16 1 0 2.597889-0.166701 0.530944 17 7 0 3.654061 2.509408-1.050902 18 6 0-3.054040 0.876585-0.083754 19 1 0-2.660973-0.033694-0.497544 20 7 0-3.481327 2.906785 0.712666 21 6 0 5.365164-0.373554-0.122590 22 6 0 5.196651-1.716582-0.490905 23 6 0 6.548395 0.036421 0.484773 24 6 0 6.205543-2.669854-0.230279 25 6 0 7.555267-0.897138 0.730641 26 1 0 6.686181 1.073777 0.761917 27 6 0 7.389900-2.239494 0.387411 28 1 0 8.164952-2.963826 0.586381 27

29 6 0-5.389862 0.023476 0.323248 30 6 0-6.047946-0.202103 1.528490 31 6 0-5.774893-0.680820-0.827057 32 6 0-7.081128-1.137962 1.583361 33 6 0-6.810609-1.639422-0.775462 34 6 0-7.458909-1.858643 0.449775 35 1 0-8.252367-2.588893 0.494722 36 1 0-5.760526 0.346720 2.416296 37 6 0 0.155840 6.199669-0.470630 38 8 0-0.843287 6.888789-0.428119 39 8 0 1.399398 6.702079-0.630747 40 6 0 1.471236 8.131500-0.753373 41 1 0 1.066705 8.613809 0.139684 42 1 0 2.529618 8.362598-0.869493 43 1 0 0.905076 8.471051-1.624079 44 6 0-7.748549-1.344019 2.906267 45 8 0-7.427199-0.765363 3.924436 46 8 0-8.747245-2.246024 2.841623 47 6 0 8.803013-0.400031 1.389533 48 8 0 8.973713 0.751639 1.735021 49 8 0 9.717161-1.375095 1.557383 50 6 0-9.434427-2.492605 4.080320 51 1 0-10.197951-3.233822 3.847683 52 1 0-8.740990-2.875199 4.832896 53 1 0-9.889838-1.572674 4.454153 54 6 0 10.943362-0.967223 2.187991 55 1 0 10.746663-0.576030 3.188910 56 1 0 11.557675-1.865251 2.239205 57 1 0 11.438096-0.193335 1.596607 58 17 0 3.734376-2.226069-1.323094 59 17 0-4.992950-0.348663-2.366088 60 17 0-0.018144 0.184576 0.011196 61 7 0-7.156530-2.319909-1.949295 62 6 0-8.129716-3.290208-2.133125 63 1 0-6.636739-2.044008-2.770318 64 8 0-8.834966-3.728625-1.239641 65 7 0 5.988774-3.999810-0.610665 66 6 0 6.828374-5.092306-0.456898 67 1 0 5.108164-4.172147-1.074291 68 8 0 7.920129-5.044356 0.085048 69 6 0-8.270042-3.746050-3.576395 70 1 0-8.643614-4.770277-3.578386 71 1 0-9.006758-3.115019-4.085469 72 1 0-7.331962-3.697997-4.136801 73 6 0 6.279540-6.373811-1.062736 74 1 0 5.186685-6.409086-1.087525 75 1 0 6.650767-6.474904-2.088354 76 1 0 6.657850-7.217048-0.484034 4-unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 1.189338 0.987880 0.243213 2 6 0-0.005761 0.276076 0.013336 3 6 0-1.216194 0.949258-0.253719 4 6 0-1.205618 2.347852-0.278302 5 6 0-0.034102 3.072274-0.055650 6 6 0 1.154803 2.386704 0.199662 7 1 0-2.119147 2.890502-0.494079 8 1 0 2.065019 2.942483 0.389456 9 6 0-2.496284 0.259154-0.501898 10 6 0-3.719893 0.525035 0.074323 11 7 0-2.671970-0.738320-1.429443 12 1 0-4.020117 1.206113 0.853163 28

13 6 0 2.480335 0.330517 0.527043 14 6 0-5.962377-0.568849-0.291753 15 6 0-6.910089 0.465191-0.324016 16 6 0-6.370758-1.876488-0.044599 17 6 0-8.276193 0.202761-0.081174 18 6 0-7.721175-2.144645 0.179988 19 1 0-5.643885-2.678597-0.028949 20 6 0-8.668814-1.120318 0.172212 21 1 0-9.712083-1.327008 0.355772 22 7 0 4.560928-0.275534 0.560733 23 7 0 3.924546-0.917679 1.586806 24 7 0-3.914137-1.099617-1.452749 25 7 0-4.583001-0.330610-0.536071 26 7 0 2.681977-0.554570 1.557796 27 6 0 3.686963 0.520957-0.111646 28 1 0 3.974654 1.104635-0.971365 29 6 0 5.960873-0.414103 0.351242 30 6 0 6.523666-1.658199 0.031002 31 6 0 6.770653 0.711070 0.462130 32 6 0 7.918051-1.787719-0.155663 33 6 0 8.146135 0.593554 0.256297 34 1 0 6.345242 1.673174 0.721184 35 6 0 8.721641-0.642235-0.041002 36 1 0 9.786141-0.737555-0.192238 37 6 0-0.112436 4.559322-0.098835 38 8 0-1.135675 5.187286-0.289608 39 8 0 1.090131 5.143863 0.099898 40 6 0 8.963660 1.838626 0.380618 41 8 0 8.495136 2.935207 0.616185 42 8 0 10.278434 1.610862 0.200422 43 6 0 1.084516 6.580572 0.078720 44 1 0 2.116922 6.880469 0.255830 45 1 0 0.737217 6.948922-0.889522 46 1 0 0.430292 6.973404 0.860658 47 6 0 11.125128 2.768085 0.305585 48 1 0 12.137752 2.404810 0.135239 49 1 0 10.850301 3.512494-0.445355 50 1 0 11.037318 3.216912 1.297719 51 6 0-8.103129-3.566700 0.443919 52 8 0-7.309700-4.484819 0.489831 53 8 0-9.430143-3.715100 0.625789 54 17 0 5.493151-3.057164-0.179788 55 17 0 0.015748-1.467130 0.062574 56 17 0-6.411914 2.107221-0.707910 57 6 0-9.868823-5.059559 0.884019 58 1 0-10.949669-4.995854 1.003484 59 1 0-9.610241-5.713197 0.047691 60 1 0-9.401806-5.446561 1.792727 61 7 0 8.437446-3.050736-0.460205 62 6 0 9.754708-3.411442-0.697688 63 1 0 7.752259-3.792661-0.496906 64 8 0 10.688797-2.626397-0.694448 65 7 0-9.182929 1.269391-0.116320 66 6 0-10.553962 1.247419 0.086025 67 1 0-8.776036 2.167390-0.335758 68 8 0-11.188777 0.242824 0.361787 69 6 0 9.944561-4.901048-0.931831 70 1 0 10.107875-5.401650 0.028865 71 1 0 9.086708-5.371229-1.421163 72 1 0 10.835916-5.042107-1.543425 73 6 0-11.221091 2.600441-0.101309 74 1 0-11.594452 2.677521-1.128151 75 1 0-12.077609 2.657478 0.571404 76 1 0-10.552983 3.445616 0.086667 29

4 Variable temperature 1 H NMR experiment of 1, 2 and 4 Figure S15 Partial 1 H NMR spectra of compound 1 in C 2 D 2 Cl 4 at different temperature, [1] = 2 mm, 400M NMR. Although there is some broadening as the temperature increases, this is likely due to shimming, which is more difficult at higher temperatures. 30

Figure S16 Partial 1 H NMR spectra of compound 2 in C 2 D 2 Cl 4 at different temperature, [2] = 2 mm, 400M NMR. Although there is some broadening as the temperature increases, this is likely due to shimming, which is more difficult at higher temperatures. 31

Figure 17 Partial 1 H NMR spectra of compound 4 in C 2 D 2 Cl 4 at different temperature, [4] = 2 mm, 400M NMR. Although there is some broadening as the temperature increases, this is likely due to shimming, which is more difficult at higher temperatures. 32

5. 1 H and 13 C NMR spectra of compounds 1-28 1 H and 13 C NMR spectra of compound 5 33

1 H and 13 C NMR spectra of compound 6 34

1 H and 13 C NMR spectra of compound 7 35

1 H and 13 C NMR spectra of compound 8 36

1 H and 13 C NMR spectra of compound 9 37

1 H and 13 C NMR spectra of compound 10 38

1 H and 13 C NMR spectra of compound 11 39

1 H and 13 C NMR spectra of compound 12 40

1 H and 13 C NMR spectra of compound 13 41

1 1 H and 13 C NMR spectra of compound 15 42

1 H and 13 C NMR spectra of compound 16 43

1 H and 13 C NMR spectra of compound 17 44

1 H and 13 C NMR spectra of compound 18 45

1 H and 13 C NMR spectra of compound 19 46

1 H and 13 C NMR spectra of compound 20 47

1 H and 13 C NMR spectra of compound 21 48

1 H and 13 C NMR spectra of compound 22 49

1 H and 13 C NMR spectra of compound 23 50

1 H and 13 C NMR spectra of compound 24 51

1 H and 13 C NMR spectra of compound 25 52

1 H and 13 C NMR spectra of compound 26 53

1 H and 13 C NMR spectra of compound 27 54

1 H and 13 C NMR spectra of compound 28 55

1 H and 13 C NMR spectra of compound 1 56

1 H and 13 C NMR spectra of compound 2 57

1 H and 13 C NMR spectra of compound 3 58

1 H and 13 C NMR spectra of compound 4 59