Supporting Infromation

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1 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 , China # College of Chemistry, Beijing Normal University, Beijing , China, Department of Chemistry, University of Nebraska, Lincoln, Nebraska University of Chinese Academy of Sciences, Beijing , China. *To whom correspondence should be addressed. hjiang@iccas.ac.cn and windsyn@iccas.ac.cn Contents 1. 1D and 2D NMR studies of compounds Crystal data of compounds 1 and Computational Details Variable temperature 1 H NMR experiment of 1, 2 and H and 13 C NMR spectra of compounds

2 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

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

4 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 H 10 d He 1 N N N H H H CO 2 i Bu 4

5 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

6 1 CO i 2 Bu ah H 3 2 3' N 4 N N N N 5 N Hc 7 6 F i H H b BuO 2 C 12 F F H H H d e F F NN N Hh N N N 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

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

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

9 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

10 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 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

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

12 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 Temperature Wavelength Crystal system, space group 173(2) K A Monoclinic, P2(1)/c Unit cell dimensions a = (19) A alpha = 90 deg. b = (3) A beta = 98.20(3) deg. c = (6) A gamma = 90 deg. Volume (12) A^3 Z, Calculated density 4, Mg/m^3 Absorption coefficient F(000) 1504 Crystal size Theta range for data collection Limiting indices mm^ x 0.12 x 0.11 mm 2.13 to deg. -11<=h<=11, -15<=k<=15, -33<=l<=31 Reflections collected / unique / 6214 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Data / restraints / parameters 6214 / 0 / 475 Goodness-of-fit on F^ Full-matrix least-squares on F^2 Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.a^-3 12

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

14 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

15 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 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 ( 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

16 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* < unfolded * folded core 2-folded edges 2-22 (folded region) (unfolded region) (folded region) (unfolded region) 3-18 (folded region) (folded region) (unfolded region) (unfolded region) unfolded * unfolded * unfolded *= ground state conformation; 1 Hartree = kcal mol 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

17 unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

18 * (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

19

20 folded core: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

21

22 2-folded edges: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

23 unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

24

25 * (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

26 unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

27 * (ground state conformation): Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

28 unfolded: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

29

30 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

31 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

32 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

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

34 1 H and 13 C NMR spectra of compound 6 34

35 1 H and 13 C NMR spectra of compound 7 35

36 1 H and 13 C NMR spectra of compound 8 36

37 1 H and 13 C NMR spectra of compound 9 37

38 1 H and 13 C NMR spectra of compound 10 38

39 1 H and 13 C NMR spectra of compound 11 39

40 1 H and 13 C NMR spectra of compound 12 40

41 1 H and 13 C NMR spectra of compound 13 41

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

43 1 H and 13 C NMR spectra of compound 16 43

44 1 H and 13 C NMR spectra of compound 17 44

45 1 H and 13 C NMR spectra of compound 18 45

46 1 H and 13 C NMR spectra of compound 19 46

47 1 H and 13 C NMR spectra of compound 20 47

48 1 H and 13 C NMR spectra of compound 21 48

49 1 H and 13 C NMR spectra of compound 22 49

50 1 H and 13 C NMR spectra of compound 23 50

51 1 H and 13 C NMR spectra of compound 24 51

52 1 H and 13 C NMR spectra of compound 25 52

53 1 H and 13 C NMR spectra of compound 26 53

54 1 H and 13 C NMR spectra of compound 27 54

55 1 H and 13 C NMR spectra of compound 28 55

56 1 H and 13 C NMR spectra of compound 1 56

57 1 H and 13 C NMR spectra of compound 2 57

58 1 H and 13 C NMR spectra of compound 3 58

59 1 H and 13 C NMR spectra of compound 4 59