Supporting information

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1 Supporting information Evidence of nanotubular self-organization in solution and solid states of heterochiralcyclo 1:1 [α/α-n α -Bnhydrazino]mers series Ralph-Olivier Moussodia, Samir Acherar,*, Eugénie Romero, Claude Didierjean, and Brigitte Jamart-Grégoire*, Laboratoire de Chimie Physique Macromoléculaire (LCPM), Université de Lorraine-CNRS, UMR 7375, 1 rue Grandville, BP 20451, Nancy cedex, France Laboratoire de Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine- CNRS, UMR 7036, Faculté des Sciences et Technologies, BP 20239, 54506Vandœuvre-lès-Nancy cedex, France Samir.Acherar@univ-lorraine.fr and Brigitte.Jamart@univ-lorraine.fr S1

2 Table of contents 1 H NMR (300 MHz) spectrum of 3 (10 mm in CDCl 3 at 298 K) S3 13 C NMR (75 MHz) spectrum of 3 (CDCl 3 at 298 K) S3 Portion of the 2D NOESY NMR (300 MHz) spectrum of 3 (10 mm in CDCl 3 at 298 K) S4 Rheological data of 3 S5 1 H NMR (300 MHz) spectrum of 4 (10 mm in CDCl 3 at 298 K) S6 13 C NMR (75 MHz) spectrum of 4 (CDCl 3 at 298 K) S6 IR spectra (deconvolution) of 3 in gel state (8.6 mm in d 8 -toluene at 298 K) S7 ATR-FTIR spectra (deconvolution) of 3 in gel state (Xerogel at 298 K) S8 Crystallographic data of 3 S9 ORTEP view of 3 S10 Method for the preparation of Aerogel S11 S2

3 1 H NMR spectrum for compound 3 recorded in CDCl 3 (10 mm) 13 C NMR spectrum for compound 3 recorded in CDCl 3 S3

4 Portion of the 2D NOESY spectrum and representation of auto-structuration observed in compound 3 (10 mm in CDCl 3 ) S4

5 Rheological data of 3 Rheological data were obtained using a rheometer at a frequency of 1 rad/s. Rheogram showing the elastic (G ) and viscous (G ) moduli of 3 as a function of temperature in d 8 -toluene solution at c = 8.6 mm S5

6 1 H NMR spectrum for compound 4 recorded in CDCl 3 (10 mm) 13 C NMR spectrum for compound 4 recorded in CDCl 3 S6

7 (1) Levenberg-Marquardt Algorithm, (2) RMSE: Root-Mean-Squared Error Deconvolution of the IR spectra of 3 in gel state at 298K (d 8 -toluene, c = 8.6 mm). a) NH stretch region and b) CO stretch region S7

8 (1) Levenberg-Marquardt Algorithm, (2) RMSE: Root-Mean-Squared Error Deconvolution of the IR (ATR-FTIR) spectra of 3 in gel state at 298 K (Xerogel). a) NH stretch region and b) CO stretch region S8

9 Crystallographic data Crystals for compound 3 exhibited weak diffracting power. Their X-ray data were collected at 100K with a diffractometer equipped with a molybdenum microsource (λ = Å). Diffraction data were processed using CrysAlis RED (Oxford Diffraction, 2011). The structure was solved by direct methods with SIR2004 (Burla M.C., Caliandro R., Camalli M., Carrozzini B., Cascarano G.L., De Caro L., Giacovazzo C., Polidori G. and Spagna R. J. Appl. Cryst. 2005, 38: ) and the crystallographic refinements were conducted using SHELXL-97 (Sheldrick G.M. Acta Cryst. 2008, A64: ). Selected crystallographic data are provided in the Table S1. Table S1. Selected crystallographic data for 3 Compound 3 Molecular formula C 32 H 46 N 6 O 4 Mr Space group C2 a (2) b (4) c (2) beta (1) Volume (7) Dx (g.cm -3 ) Z 8 F(000) Nref (measured) R int Data completeness 0.99 Theta(max) 21.2 R 1 (F 2 >2σ(F 2 ) (3052) wr 2 (all data) 0.312(3844) S 1.31 N par 751 S9

10 ORTEP view of compound 3. One-half of the unit cell is shown and the H atoms, except those of the NH groups and methine, are omitted for clarity S10

11 Method for the preparation of Aerogel The drying of organogel by supercritical CO 2 was performed using the following procedure: a sample of organogel is introduced in the autoclave.supercritical drying is performed following two steps according to the thermodynamic data : a static step followed by a dynamic or continuous supercritical drying. The conditions of the first step for a toluene organogel was those of liquid CO 2 ( T=15 C, P= 90 bars with a contact duration between organogel and CO 2 of 15 minutes). Then the temperature was increasing at 45 C (P=90 bars, solvant:toluene, duration: 20 minutes). In the second step, the system is in supercritical state and the solvent extraction can be performed. According to a CO 2 flowrate near 350 g/h, the drying need 210 minutes. At the end of the procedure, the pressure is first released to atmospheric pressure and the aerogel is extracted out of the autoclave. CO 2 supercritical drying process S11