Supporting Information. Liquid-Crystalline Dendrimers Designed by Click Chemistry

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1 S1 Supporting Information Liquid-Crystalline Dendrimers Designed by Click Chemistry Sebastiano Guerra, Thi Le Anh Nguyen, Julien Furrer, Jean-François Nierengarten,*, Joaquín Barberá,*, and Robert Deschenaux*, Institut de Chimie, Université de Neuchâtel, Avenue de Bellevaux 51, CH-2000 Neuchâtel, Switzerland Laboratoire de Chimie des Matériaux Moléculaires, Université de Strasbourg et CNRS (UMR 7509), Ecole Européenne de Chimie, Polymères et Matériaux, 25 rue Becquerel, Strasbourg Cedex 2, France Departamento de Química rgánica, Facultad de Ciencias-Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, Zaragoza, Spain General. CH 2 Cl 2 was distilled over P 2 5 under Ar. All reagents were purchased from Sigma- Aldrich and used as received. Compounds 8, 1 9, and 11 4 were prepared according to literature procedures. Column chromatography used silica gel Brunschwig ( nm). NMR spectra were recorded on a Bruker Avance II 400 MHz spectrometer, equipped with a 5 mm dual-channel broadband (BBF) probehead or on a Bruker Avance II 600 MHz spectrometer equipped with a 5 mm triple ( 1 H, 13 C, 15 N) cryoprobehead. The experiments were recorded at a regulated temperature of 25 C and the solvent was used as internal reference. Mass spectra were recorded on a Finnigan LCQ for ESI experiments, or on a Bruker FTMS 4.7T BioAPEX II for the MALDI-MS experiments. IR spectra were recorded on a FT-IR Spectrometer PerkinElmer Spectrum ne. Elemental analyses were performed by the Mikroelementaranalytisches Laboratorium, ETH-Zurich. Transition temperatures (onset point) and enthalpies were determined with a differential scanning Mettler DSC 822 e calorimeter, under N 2 /He, at rate of 10 C/min. ptical studies were conducted using a Zeiss- Axioscope polarizing microscope equipped with a Linkam-THMS-600 variable-temperature stage a Linkam-TMS-91 temperature controller. The XRD patterns were obtained with a pinhole camera (Anton-Paar) operating with a point-focused Ni-filtered Cu-Kα beam. The samples were held in Lindemann glass capillaries (1 mm diameter) and heated, when necessary, with a variable-temperature oven. The capillary was vertically exposed to the X- ray beam, and the patterns were collected on a flat photographic film perpendicular to the beam. Spacings were obtained via Bragg s law. Abbreviations. Column chromatography = CC; 4-(dimethylamino)pyridinium toluene-psulfonate = DPTS; N,N -dicyclohexylcarbodiimide = DCC; N-(3-dimethylaminopropyl)-N - ethylcarbodiimide = EDC; 4-pyrrolidinopyridine = 4-ppy.

2 S2 (CH2)10 C 2 CN (CH2)10 C 2 CN H (CH2)10 C 2 CN C 2 (CH2)10 CN H N C 12 H 25 C 12 H 25 C 12 H 25 C 12 H 25 C 12 H 25 C 12 H 25 H (CH2)6 2 C HC C 12 H 25 C 12 H 25 C 12 H 25 C 12 H 25 C 12 H 25 C 12 H Figure S1. Structures of compounds Synthesis of alkyne precursors To a mixture of the corresponding phenol or alcohol derivative, 4-pentynoic acid and DPTS in dry CH 2 Cl 2 at 0 C, were added DCC or EDC and 4-ppy (spatula tip). The mixture was stirred at room temperature overnight under Ar. The mixture was washed (H 2 ), dried (MgS 4 ), filtered and evaporated to dryness. Purification of the residue by CC (Si 2 ; CH 2 CH 2 or CH 2 Cl 2 /AcEt 100:2) gave pure 4 or 5. Compound 4. From 8 (1.0 g, 0.43 mmol), 4-pentynoic acid (46.0 mg, 0.47 mmol), DPTS (139.0 mg, 0.47 mmol) and DCC (133.0 mg, 0.65 mmol) in CH 2 Cl 2 (20 ml); yield: mg (63%). 1 H NMR (δ in ppm, 400 MHz, CD 2 Cl 2 ): 8.91 (t, 1H, arom. H), 8.64 (t, 2H, arom. H), 8.24 (d, 2H, arom. H), 8.14 (d, 8H, arom. H), 8.10 (d, 4H, arom. H), 7.73 and 7.68 (2d, AB system, 16H, arom. H), 7.63 (d, 8H, arom. H), 7.32 (d, 8H, arom. H), 6.97 (d, 8H, arom. H), 4.36 (t, 8H, C 2 CH 2 ), 4.03 (t, 8H, CH 2 Ar), 2.90 (t, 2H, CH 2 C 2 ), 2.68 (td, 2H, CH 2 C C), 2.08 (t, 1H, C CH), (m, 16H, CH 2 CH 2 Ar and ArC 2 CH 2 CH 2 ), (m, 48H, aliph. H). 13 C NMR (δ in ppm, 100 MHz, CD 2 Cl 2 ): , , , , , , , , , , , , , , , , , , , , , , , , , 81.94, 69.49, 68.53, 65.96, 33.47, 29.55, 29.52, 29.40, 29.32, 29.17, 28.71, 26.05, 26.02, MS (ESI):

3 S [M+Na] +. Anal. Calcd for C 149 H 142 N 4 26 ( ): C 74.42, H 5.95, N 2.33%; found: C 74.26, H 5.99, N 2.31%. Compound 5. From 9 (600.0 mg, 0.26 mmol), 4-pentynoic acid (28.0 mg, 0.29 mmol), DPTS (85.0 mg, 0.29 mmol) and EDC (0.06 ml, 0.31 mmol) in CH 2 Cl 2 (20 ml); yield: mg (69%). 1 H NMR (δ in ppm, 400 MHz, CD 2 Cl 2 ): 7.44 (d, 2H, arom. H), 7.32 (d, 8H, arom. H), 7.24 (d, 4H, arom. H), 7.12 (d, 2H, arom. H), 6.92 (d, 2H, arom. H), 6.89 (d, 9H, arom. H), 6.77 (s, 4H, arom. H), 6.74 (d, 4H, arom. H), 5.03 (s, 4H, 2xCH 2 Ar), 5.00 (s, 8H, 4xCH 2 Ar), 4.89 (s, 4H, 2xCH 2 Ar), 4.10 (t, 2H, C 2 CH 2 ), (m, 14H, CH 2 Ar), (m, 4H, CH 2 CH 2 C C), 2.02 (t, 1H, C CH), (m, 14H, CH 2 CH 2 Ar), (m, 114H, aliph. H), 0.90 (t, 18H, CH 3 ). 13 C NMR (δ in ppm, 100 MHz, CD 2 Cl 2 ): , , , , , , , , , , , , , , , , , , , , , , 82.80, 74.76, 71.03, 70.61, 68.69, 68.40, 68.19, 68.10, 64.71, 33.45, 32.03, 29.78, 29.75, 29.73, 29.55, 29.46, 29.43, 29.41, 29.27, 28.67, 26.15, 25.81, 22.79, 14.39, MS (ESI): [M+H 2 +H] +. Anal. Calcd for C 152 H ( ): C 77.71, H 9.35%; found: C 77.52, H 9.36%. Synthesis of azide precursors Compound 6. To a mixture of 10 (1.0 g, 4.69 mmol), terephthalic acid (389.0 mg, 2.34 mmol) and DPTS (690.0 mg, 2.34 mmol) in dry CH 2 Cl 2 (50 ml) at 0 C, were added DCC (1.45 g, 7.03 mmol) and 4-ppy (spatula tip). The mixture was stirred at room temperature for 24 hours under Ar, washed (H 2 ), dried (MgS 4 ), filtered and evaporated to dryness. Purification of the residue by CC (Si 2, CH 2 Cl 2 ) gave pure 6 (936.0 mg, 72%). 1 H NMR (δ in ppm, 400 MHz, CDCl 3 ): 8.10 (s, 4H, arom. H), 4.34 (t, 4H, C 2 CH 2 ), 3.26 (t, 4H, CH 2 N 3 ), (m, 4H, C 2 CH 2 CH 2 ), (m, 4H, CH 2 CH 2 N 3 ), (m, 28H, aliph. H). 13 C NMR (δ in ppm, 100 MHz, CDCl 3 ): , , , 65.69, 51.61, 29.58, 29.56, 29.36, 29.25, 28.96, 28.78, 26.83, IR (KBr, ν in cm -1 ): 2094 (N 3 ). MS (ESI): [M+Na] +. Anal. Calcd for C 30 H 48 N 6 4 (556.74): C 64.72, H 8.69, N 15.09%; found C 64.90, H 8.76, N 14.91%. Compound 7. To a mixture of 11 (100.0 mg, 0.05 mmol), 10 (11.0 mg, 0.05 mmol) and DPTS (15.0 mg, 0.05 mmol) in dry CH 2 Cl 2 (20 ml) at 0 C, were added DCC (52.0 mg, 0.25 mmol) and 4-ppy (spatula tip). The mixture was stirred at room temperature overnight under Ar, washed (brine), dried (MgS 4 ), filtered and evaporated to dryness. Purification of the residue by CC (Si 2, CH 2 Cl 2 /n-heptane 3:2) gave pure 7 (48.0 mg, 42 %). 1 H NMR (δ in ppm, 400 MHz, CD 2 Cl 2 ): 7.33 (d, 8H, arom. H), 7.29 (d, 2H, arom. H), 7.23 (d, 4H, arom. H), 6.88 (d, 8H, arom. H), 6.79 (t, 1H, arom. H), 6.76 (s, 4H, arom. H), 6.74 (d, 4H, arom. H), 5.00 (s, 8H, 4xCH 2 Ar), 4.99 (s, 4H, 2xCH 2 Ar), 4.88 (s, 4H, 2xCH 2 Ar), 4.29 (t, 2H, C 2 CH 2 ), (m, 12H, CH 2 CH 2 Ar), 3.24 (t, 2H, N 3 CH 2 ), (m, 14H, 6xCH 2 CH 2 Ar and C 2 CH 2 CH 2 ), (m, 124H, aliph. H), 0.88 (t, 18H, CH 3 ). 13 C NMR (δ in ppm, 100 MHz, CD 2 Cl 2 ): , , , , , , , , , , , , 74.76, 71.01, 70.54, 68.19, 68.09, 55.77, 51.61, 35.08, 32.03, 29.79, 29.75, 29.56, 29.47, 29.42, 29.24, 28.91, 28.80, 26.79, 26.16, 25.59, 24.81, 22.80, IR (KBr, ν in cm -1 ): 2094 (N 3 ). MS (ESI): [M+H 2 +H] +. Anal. Calcd for C 146 H 219 N 3 16 ( ): C 77.17, H 9.71, N 1.85%; found: C 77.09, H 9.63, N 1.93%.

4 S δ 5.0 (ppm) Figure S2. 1 H NMR spectrum (400 MHz) of 4 in CDCl 3.

5 S δ 4.0 (ppm) Figure S3. 1 H NMR spectrum (400 MHz) of 5 in CD 2 Cl 2.

6 S δ (ppm) Figure S4. 1 H NMR spectrum (400 MHz) of 6 in CDCl 3.

7 S δ 4.0 (ppm) Figure S5. 1 H NMR spectrum (400 MHz) of 7 in CD 2 Cl 2.

8 S δ (ppm) Figure S6. 1 H NMR spectrum (600 MHz) of 1 in CD 2 Cl 2.

9 S δ 4.5 (ppm) Figure S7. 1 H NMR spectrum (600 MHz) of 2 in CD 2 Cl 2.

10 S δ 4.5 (ppm) Figure S8. 1 H NMR spectrum (600 MHz) of 3 in CD 2 Cl 2.

S11 0 50 100 150 200 Temperature ( C) Figure S9.

11 S Temperature ( C) Figure S9. Differential scanning thermograms of 1 registered during the second heating (red line) - cooling (blue line) cycle. Figure S10. Thermal-polarized optical micrograph of the focal-conic fan texture and homeotropic area displayed by 4 in the smectic A phase at 200 C.

$Powder small-angle X-ray diffraction pattern of 4 in the smectic A phase; the sample was heated$ into the isotropic fluid, and cooled to 25 C. 4.5 Å 39.2 Å (1 1) 32.2 Å, weak (2 0) 25.

into the isotropic fluid, and cooled to 25 C. 4.5 Å 39.2 Å (1 1) 32.2 Å, weak (2 0) 25.

12 S12 57 Å (very weak) Å Figure S11. Powder small-angle X-ray diffraction pattern of 4 in the smectic A phase; the sample was heated into the isotropic fluid, and cooled to 25 C. 4.5 Å 39.2 Å (1 1) 32.2 Å, weak (2 0) 25.4 Å, weak (0 2) Figure S12. Powder small-angle X-ray diffraction pattern and indexation of the reflections of the rectangular columnar phase for 5 at 60 C.

$Powder small-angle X-ray diffraction pattern and indexation of the reflections$ of the rectangular columnar phase for 7 at 70 C. 77.6 Å 39.1 Å 31.7 Å 26.

13 S Å 40.9 Å (1 1) 31.8 Å (2 0) Figure S13. Powder small-angle X-ray diffraction pattern and indexation of the reflections of the rectangular columnar phase for 7 at 70 C Å 39.1 Å 31.7 Å 26.0 Å (weak) Figure S14. Powder small-angle X-ray diffraction pattern of 2 in the rectangular columnar phase at 70 C.

$Powder small-angle X-ray diffraction pattern of 3 in the$ rectangular columnar phase at 55 C. 110 Å 4.4 Å 55.3 Å 37.5 Å 27.

14 S Å 44.4 Å 34.4 Å 26.1 Å Figure S15. Powder small-angle X-ray diffraction pattern of 3 in the rectangular columnar phase at 55 C. 110 Å 4.4 Å 55.3 Å 37.5 Å 27.7 Å 22.4 Å Figure S16. Powder small-angle X-ray diffraction pattern of 3 in the smectic A phase at 90 C.

15 S15 b r a r Figure S17. Representation of the centered rectangular columnar phase of c2mm symmetry. References (1) Dardel, D.; Guillon, D.; Heinrich, B.; Deschenaux, R. Fullerene-Containing Liquid Crystalline Dendrimers. J. Mater. Chem. 2001, 11, (2) Campidelli, S.; Lenoble, J.; Barberá, J.; Paolucci, M. M.; Paolucci, D.; Deschenaux, R. Supramolecular Fullerene Materials: Dendritic Liquid-Crystalline Fulleropyrrolidines. Macromolecules 2005, 38, (3) Guerra, S.; Iehl, J.; Holler, M.; Peterca, M.; Wilson, D. A.; Partridge, B. E.; Zhang, S.; Deschenaux, R.; Nierengarten, J.-F.; Percec, V. Self-rganization of Dodeca-Dendronized Fullerene into Supramolecular Discs and Helical Columns Containing a Nanowire-Like Core. Chem. Sci. 2015, 6, (4) Percec, V.; Cho, W.-D.; Ungar, G.; Yeardley, D. J. P. Synthesis and Structural Analysis of Two Constitutional Isomeric Libraries of AB 2 -Based Monodendrons and Supramolecular Dendrimers. J. Am. Chem. Soc. 2001, 123,

Fullerene-containing liquid-crystalline dendrimers{

Fullerene-containing liquid-crystalline dendrimers{ Blaise Dardel, a Daniel Guillon,* b Benoît Heinrich b and Robert Deschenaux* a a Institut de Chimie, Université de Neuchâtel, Avenue de Bellevaux 51,