Supporting Information Identification of Absolute Helical Structures of Aromatic Multi-layered Oligo(m-phenylurea)s in Solution. Mayumi Kudo, 1 Takayuki Hanashima, 2 Atsuya Muranaka, 3,* Hisako Sato, 4,5, Masanobu Uchiyama, 3 Isao Azumaya, 6 Tomoya Hirano, 2 Hiroyuki Kagechika, 2 and Aya Tanatani 1,5,* Content page General experimental methods 2 Figure S1. NMR charts of new compounds (a) 1 H and 13 C NMR of Compound 10 3 (b) 1 H and 13 C NMR of Compound 11 4 (c) 1 H and 13 C NMR of Compound 12 5 (d) 1 H and 13 C NMR of Compound 13 6 (e) 1 H and 13 C NMR of Compound 14 7 (f) 1 H and 13 C NMR of Compound 15 8 (g) 1 H and 13 C NMR of Compound 16 9 (h) 1 H and 13 C NMR of Compound 4 10 (i) 1 H and 13 C NMR of Compound 17 11 Figure S2. Temperature-dependent 1 H NMR (a) Temperature-dependent 1 H NMR of 4 12 (b) Temperature-dependent 1 H NMR of 17 12 Figure S3. CD and UV spectra of compound 17 13 Table S1. Atomic coordinates of the optimized structure of 3 14 Figure S4. Calculated spectra for the X-ray structure of 3 with all-r axis chirality 18 Figure S5. VCD and IR spectra of 4a and 4b in CDCl 3 19 Figure S6. Calculated VCD spectrum of 18 20 The full list of authors for reference 32. 21-1 -
General experimental methods 1 H and 13 C NMR spectra were recorded at 400, 500, or 600 MHz. Mass spectral data were obtained in the positive and negative ion detection modes. Melting points were taken on a micro melting point apparatus and are uncorrected. Elemental analyses were carried out using an elemental analyzer. UV spectra were recorded with a double-beam spectrophotometer. CD spectra were recorded with a spectropolarimeter using 2 mm quartz cell. The concentration of each solution of CD experiments was adjusted so that the absorbance of the oligoureas was 1 at the maximum absorption wavelength in the examined solvents. - 2 -
Figure S1. NMR charts of new compounds (a) 1 H and 13 C NMR of Compound 10 1 H NMR in CDCl 3 13 C NMR in CDCl 3-3 -
(b) 1 H and 13 C NMR of Compound 11 1 H NMR in CDCl 3 13 C NMR in CDCl 3-4 -
(c) 1H and 13C NMR of Compound 12 1 H NMR in DMSO-d6 13 C NMR in DMSO-d6-5-
(d) 1 H and 13 C NMR of Compound 13 1 H NMR in CDCl 3 13 C NMR in CDCl 3-6 -
(e) 1H and 13C NMR of Compound 14 1 H NMR in CDCl3 13 C NMR in CDCl3-7-
(f) 1H and 13C NMR of Compound 15 1 H NMR in CDCl3 13 C NMR in CDCl3-8-
(g) 1H and 13C NMR of Compound 16 1 H NMR in CDCl3 13 C NMR in CDCl3-9-
(h) 1H and 13C NMR of Compound 4 1 H NMR in CDCl3 13 C NMR in CDCl3-10-
(i) 1 H and 13 C NMR of Compound 17 Compound 17: 1 H NMR (400 MHz, CDCl 3 ): δ 6.94 (t, J = 7.6 Hz, 4 H), 6.85 (t, J = 7.3 Hz, 2 H), 6.61 (d, J = 7.8 Hz, 4 H), 6.60 (t, J = 8.1 Hz, 2 H), 6.52 (t, J = 7.8 Hz, 1 H), 6.33 (d, J = 8.3 Hz, 2 H), 6.20 (d, J = 8.8 Hz, 2 H), 6.14 (dd, J = 2.0, 7.8 Hz, 2 H), 6.06 (s, 1 H), 5.98(s, 2 H), 3.43 (t, J = 7.6 Hz, 4 H), 3.28 (br m, 4 H), 3.25 (t, J = 10.0 Hz, 4 H), 3.18 (t, J = 7.8 Hz, 4 H), 1.6-1.0 (br m, 32 H), 0.89 (d, J = 6.3 Hz, 12 H), 0.87 (d, J = 6.3 Hz, 6 H), 0.88-0.81 (m, 18 H). 13 C NMR (125 MHz, CDCl 3 ) δ 160.0, 159.4, 144.9, 144.8, 144.6, 144.0, 128.2, 127.7, 127.6, 126.4, 124.7, 123.7, 123.2, 123.0, 122.7, 122.1, 60.4, 53.4, 50.4, 39.3, 37.3, 36.1, 31.2, 28.0, 24.8, 22.8, 22.7, 21.6, 21.5, 21.1, 19.5, 14.3, 11.5, 11.4. HRMS (ESI+) calcd for C 72 H 106 N 8 NaO 4 (M + +Na) 1169.8229, found 1169.8245. 1 H NMR 13 C NMR - 11 -
Figure S2. Temperature-dependent 1 H NMR of 4 and 17 in CDCl 3. (a) Compound 4 in CDCl 3 (b) Compound 17 in CDCl 3-12-
Figure S3. (a) CD and (b) UV spectra of compound 17. - 13-
Table S1. Atomic coordinates of the optimized structure of N-methylated oligo(phenylurea) 3 with all-r axis chirality (B3LYP/6-31G**). ----------------------------------------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ----------------------------------------------------------------------------------------------------- 1 6 0-2.58758 1.647596-1.54293 2 1 0-2.84506 2.360312-2.32654 3 1 0-2.46773 0.651728-1.97164 4 1 0-3.41123 1.626047-0.81841 5 8 0-6.78496-1.98815 1.058045 6 8 0 2.188964-4.16263-0.72065 7 8 0-2.18896 4.162626-0.72065 8 8 0 6.784957 1.988149 1.058045 9 7 0-6.05782-3.95864 0.133404 10 7 0-4.5229-2.29725 0.84979 11 7 0-1.32196 2.049849-0.91463 12 7 0 0 3.855277-0.11464 13 7 0 6.057816 3.95864 0.133404 14 7 0 4.522895 2.297246 0.84979 15 7 0 1.321962-2.04985-0.91463 16 7 0 0-3.85528-0.11464 17 6 0-3.59012-7.31651 0.892969 18 6 0-3.96188-6.47347 1.942473 19 6 0-4.76847-5.36135 1.700476 20 6 0-5.19139-5.06945 0.397618 21 6 0-7.45984-4.28891-0.15098 22 6 0-5.85167-2.70109 0.704997 23 6 0-3.51784-2.62297-0.11862 24 6 0-3.74354-2.43404-1.48803 25 6 0-2.72674-2.71231-2.40129 26 6 0-2.26814-3.06757 0.319173 27 6 0-1.24623-3.33713-0.59528 28 6 0-1.48286-3.16785-1.96503 29 6 0-0.01297-5.24997 0.347259 30 6 0 1.232681-3.40584-0.59098 31 6 0 2.587584-1.6476-1.54293-14-
Table S1. (continued). ----------------------------------------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ----------------------------------------------------------------------------------------------------- 32 6 0 0.632714-1.03706-0.17296 33 6 0 0.641573-1.02909 1.227787 34 6 0 0 0 1.917512 35 6 0-0.64157 1.029088 1.227787 36 6 0-0.63271 1.03706-0.17296 37 6 0 0 0-0.8635 38 6 0-1.23268 3.405844-0.59098 39 6 0 0.012968 5.249972 0.347259 40 6 0 1.246231 3.337125-0.59528 41 6 0 1.482856 3.167848-1.96503 42 6 0 2.726738 2.712311-2.40129 43 6 0 3.743537 2.434044-1.48803 44 6 0 3.51784 2.622969-0.11862 45 6 0 2.268143 3.067566 0.319173 46 6 0 4.334211 1.037445 1.580502 47 6 0 5.851667 2.701093 0.704997 48 6 0 7.459836 4.288907-0.15098 49 6 0 5.191385 5.069449 0.397618 50 6 0 4.768471 5.361349 1.700476 51 6 0 3.961881 6.473465 1.942473 52 6 0 3.590121 7.316513 0.892969 53 6 0 4.022426 7.034154-0.40452 54 6 0-4.81349-5.91353-0.65304 55 6 0-4.02243-7.03415-0.40452 56 6 0 4.813493 5.913525-0.65304 57 6 0-4.33421-1.03745 1.580502 58 1 0-2.97203-8.18836 1.085194 59 1 0-3.63981-6.69151 2.956727 60 1 0-5.0732-4.71574 2.5179 61 1 0-7.95506-3.4171-0.5776 62 1 0-7.49005-5.11515-0.86342 63 1 0-8.00241-4.58152 0.756696-15-
Table S1. (continued). ----------------------------------------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ----------------------------------------------------------------------------------------------------- 64 1 0-4.70968-2.07628-1.82828 65 1 0-2.90698-2.57767-3.46392 66 1 0-2.09092-3.20787 1.379802 67 1 0-0.69652-3.39294-2.67774 68 1 0-0.92533-5.42349 0.919199 69 1 0 0.018953-5.95535-0.49223 70 1 0 0.85933-5.43002 0.975757 71 1 0 3.411233-1.62605-0.81841 72 1 0 2.845063-2.36031-2.32654 73 1 0 2.467733-0.65173-1.97164 74 1 0 1.143749-1.82574 1.766318 75 1 0 0 0 3.003764 76 1 0-1.14375 1.825743 1.766318 77 1 0 0 0-1.94802 78 1 0-0.01895 5.955353-0.49223 79 1 0-0.85933 5.430019 0.975757 80 1 0 0.92533 5.423493 0.919199 81 1 0 0.69652 3.392939-2.67774 82 1 0 2.906983 2.577666-3.46392 83 1 0 4.709675 2.076278-1.82828 84 1 0 2.090924 3.207874 1.379802 85 1 0 3.280501 0.938794 1.845494 86 1 0 4.632374 0.169319 0.97919 87 1 0 4.94412 1.048304 2.484087 88 1 0 8.002407 4.581522 0.756696 89 1 0 7.95506 3.417095-0.5776 90 1 0 7.490048 5.115146-0.86342 91 1 0 3.639809 6.69151 2.956727 92 1 0 2.97203 8.188357 1.085194 93 1 0 3.734616 7.681573-1.22762 94 1 0-5.1324-5.67607-1.66304 95 1 0-3.73462-7.68157-1.22762-16-
Table S1. (continued). ----------------------------------------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ----------------------------------------------------------------------------------------------------- 96 1 0 5.132396 5.676071-1.66304 97 1 0-4.94412-1.0483 2.484087 98 1 0-3.2805-0.93879 1.845494 99 1 0-4.63237-0.16932 0.97919 100 1 0 5.073202 4.715735 2.5179 ----------------------------------------------------------------------------------------------------- - 17-
Figure S4. Calculated spectra for the X-ray structure of N-methylated oligo(phenylurea) 3 with all-r axis chirality obtained using the ZINDO/S method. Gaussian bands with a half-bandwidth of 3000 cm 1 were used. - 18-
Figure S5. (a) VCD and (b) IR spectra of 4a (blue line) and 4b (red line) in CDCl 3. The signals indicated with arrows could be reproducibly observed as negative and positive peaks for 4a and 4b, respectively, although their intensity was small. - 19-
Figure S6. (a) Calculated structure of tetraurea 18, a derivative of 3 (all-r axis chirality) bearing two chiral N-(S)-2-methoxy-1-propyl substituents (b) Calculated VCD spectrum of 18 in comparison with (c) the experimental VCD spectrum of 4a. No correction of introducing a scale factor was made in the calculated spectra. - 20-
The full list of authors for reference 32. Fisch, M. J.; Trucks,G. W.; Schlegel, H. B.; Scuseria,G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, Jr. 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.; 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. Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004. - 21-