Supporting Information. Identification of Absolute Helical Structures of Aromatic Multi-layered Oligo(m-phenylurea)s in Solution.

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1 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 Figure S2. Temperature-dependent 1 H NMR (a) Temperature-dependent 1 H NMR of 4 12 (b) Temperature-dependent 1 H NMR of Figure S3. CD and UV spectra of compound 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 The full list of authors for reference

2 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

3 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 -

4 (b) 1 H and 13 C NMR of Compound 11 1 H NMR in CDCl 3 13 C NMR in CDCl 3-4 -

5 (c) 1H and 13C NMR of Compound 12 1 H NMR in DMSO-d6 13 C NMR in DMSO-d6-5-

6 (d) 1 H and 13 C NMR of Compound 13 1 H NMR in CDCl 3 13 C NMR in CDCl 3-6 -

7 (e) 1H and 13C NMR of Compound 14 1 H NMR in CDCl3 13 C NMR in CDCl3-7-

8 (f) 1H and 13C NMR of Compound 15 1 H NMR in CDCl3 13 C NMR in CDCl3-8-

9 (g) 1H and 13C NMR of Compound 16 1 H NMR in CDCl3 13 C NMR in CDCl3-9-

10 (h) 1H and 13C NMR of Compound 4 1 H NMR in CDCl3 13 C NMR in CDCl3-10-

11 (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), (br m, 32 H), 0.89 (d, J = 6.3 Hz, 12 H), 0.87 (d, J = 6.3 Hz, 6 H), (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, HRMS (ESI+) calcd for C 72 H 106 N 8 NaO 4 (M + +Na) , found H NMR 13 C NMR

12 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-

13 Figure S3. (a) CD and (b) UV spectra of compound

14 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

15 Table S1. (continued) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

16 Table S1. (continued) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

17 Table S1. (continued) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

18 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

19 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

20 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

21 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,