Supporting Information

© Wiley-VCH 2007

69451 Weinheim, Germany

Light Driven Supramolecular Chirality in Propeller-like H-Bonded Complexes Showing Columnar Mesomorphism∗∗

Francisco Vera, Rosa M. Tejedor, Pilar Romero, Joaquín Barberá, M. Blanca Ros, José Luis Serrano*, Teresa Sierra*

[∗] Dr. Barberá, Dr. P. Romero, Dr. M. B. Ros, Prof. Dr. J. L. Serrano, Dr. T. Sierra, Dr. R. M. Tejedor, F. Vera

Química Orgánica. Facultad de Ciencias Insitituto de Ciencia de Materiales de Aragón Universidad de Zaragoza-C.S.I.C. 50009-Zaragoza. Spain. Fax: (+) 34976761209 E-mail: tsierra@unizar.es

[∗∗] This work was supported by the CICYT projects MAT2003-07806-CO2-01, MAT2005-06373-CO2-01, FEDER founding (EU) and the DGA.

Synthesis

The synthetic procedures followed for the preparation of the V-shaped acids are outlined in scheme SI1

H2N

COOEtNaNO2/HCl/H2O

30 min +N2

COOEtCl-

N

COOEt

N

HO

a) Phenolb) NaHCO3

Br(S) H2/PtO2

1 day Br(S)

Br(R) H2/PtO2

1 day Br(R)

1

2

3

N

COOEt

N

RO4

acetone/KI/reflux/

K2CO3/16h

4a: OR = O(S)

4b: OR = O(R)

4c: OR = OC14H29 = 14

N

COOH

N

RO

EtOH/KOHreflux5

N

COCl

N

RO

(COCl)2/DMFDCM / 2 h / r.t.5'

COOH

HO OHMorpholine

ClTIPSr.t. / 10 min

COOTIPS

HO OH

6

5'NEt3DCM

r.t.1 day

COOTIPS

O O

O O

NN

NN

RO OR

7

COOH

O O

O O

NN

NN

RO OR

= (S)10*

= (R)10*

5 eq TBAF, -78ºC, 3 h6 eq AcOH, r. t., 10 min

8a: R = (S)10* 8b: R = (R)10*8c: R = 14

5a, 5b, 5c5'a, 5'b, 5'c

7a, 7b, 7c

T-A(S)10*T-A(R)10*T-A14

RBr

Scheme SI1

The preparation and physical properties of compounds 1, 4c and 5c were previously reported in C.L.

Folcia, I. Alonso, J. Ortega, J. Etxebarría, I. Pintre, M.B. Ros, Chem. Mater. 2006, 18, 4617.

Compound 1. A solution of sodium nitrite (2.27 g, 32.04 mmol in 15.7 mL of water) is added drop wise

to a suspension of 4.5 g (26.70 mmol) of ethyl p-aminobenzoate in a mixture of 10 mL HCl and 30 mL of

water, keeping the temperature below 5 ºC. After 30 min. for stirring, the ammonium salt is formed.

Then, 3.05 g of phenol (32.04 mmol) is added. The reaction was stirred for 1 hour. The solution was

made basic with 100 mL of a saturated solution of NaHCO3. A brown solid precipitated, which was

filtered off and washed with distilled water. The product was isolated by recrystallization with ethanol.

The powder obtained had a red-orange intense color. Yield: 70 %. mp 164 ºC; TLC (silica gel, DCM) Rf

= 0.16. 1H-RMN (400 MHz, CDCl3): δ 8.18 (d, J = 8.4 Hz, 2H, Ar-H), 7.92 (d, J = 8.4 Hz, 2H, Ar-H),

7.90 (d, J = 8.8 Hz, 2H, Ar-H), 6.97 (d, J = 8.8 Hz, 2H, Ar-H), 5.39 (b s, 1H, OH), 4.42 (c, J = 7.2 Hz,

2H, -OCH2CH3), 1.43 (t, J = 7.2 Hz, 3H, -OCH2CH3). FT-IR (Nujol): 3500-3100 cm-1 (OH), 1692 cm-1

(C=O), 1280 cm-1 (C-O).

Compounds 2 and 3. 15 g (65.70 mmol) of (S)-8-bromo-2,6-dimethyloct-2-ene (for 2) or (R)-8-bromo-

2,6-dimethyloct-2-ene (for 3) were dissolved in 25 mL of ethyl acetate. 0.300 g of PtO2 were added to the

solution. The reaction mixture was stirred for 1 day under a pressure of 80 bar of hydrogen. The solution

was filtered through Celite®, and the solvent was evaporated. The product was a colorless liquid. Yield:

quantitative. 1H-RMN (400 MHz, CDCl3): δ 3.45-3.37 (m, 2H, -CH2Br), 1.87-1.84 (m, 1H, -CH-(CH3)2),

1.68-1.61 (m, 2H, -CH2CH2Br), 1.52-1.48 (m, 1H, -CH2-CH(CH3)-CH2-), 1.36-1.21 (m, 3H, -CH2-),

1.21-1.06 (m, 3H, -CH2-), 0.89 (d, J = 7.6 Hz, 3H, -CH(CH3)-), 0.86 (d, J = 8.0 Hz, 6H, -CH(CH3)2).

Compounds 4. General procedure. 18.5 mmol of 1, anhydrous K2CO3 (5.11 g, 37.0 mmol) and KI (0.100

g) were dissolved in 100 mL of acetone, under argon atmosphere. After 10 minutes stirring, 22.2 mmol of

compound 2 (for 4a), compound 3 (for 4b) or 1-bromo-n-tetradecane (for 4c) were added drop wise via

syringe while the solution was refluxing. The mixture was stirred overnight under reflux. After cooling

down to room temperature, 200 mL of water were added. The product was extracted with

dichloromethane. The organic layer was dried with MgSO4 and filtered, and then the solvent was

evaporated. The product was recrystallized with ethanol. The product was an orange powder. Yield: 86

%. TLC (silica gel, DCM) Rf = 0.85.

4a and 4b: 1H-RMN (400 MHz, CDCl3): δ 8.17 (d, J = 8.4 Hz, 2H, Ar-H), 7.94 (d, J = 8.4 Hz, 2H,

Ar-H), 7.89 (d, J = 8.8 Hz, 2H, Ar-H), 7.01 (d, J = 8.8 Hz, 2H), 4.41 (c, J = 7.2 Hz, 2H, -OCH2CH3), 4.08

(t, J = 6.0 Hz, 2H, -OCH2CH2-), 1.92-1.82 (m, 1H, -CH-(CH3)2), 1.76-1.60 (m, 2H, -CH2CH2O-), 1.58-

1.50 (m, 1H, -CH2-CH(CH3)-CH2-), 1.42 (t, J = 7.2 Hz, 3H, -OCH2CH3), 1.38-1.24 (m, 3H, -CH2-), 1.22-

1.11 (m, 3H, -CH2-), 0.96 (d, J = 6.8 Hz, 3H, -CH(CH3)-), 0.87 (d, J = 6.8 Hz, 6H, -CH(CH3)2). FT-IR

(Nujol): 1714 cm-1 (C=O), 1276 cm-1 (C-O), 1256 cm-1 (CAr-O).

4c: 1H-RMN (400 MHz, CDCl3): δ 8.17 (d, J = 8.4 Hz, 2H, Ar-H), 7.94 (d, J = 8.4 Hz, 2H, Ar-H),

7.89 (d, J = 8.8 Hz, 2H, Ar-H), 7.01 (d, J = 8.8 Hz, 2H, Ar-H), 4.41 (c, J = 7.2 Hz, 2H, -OCH2CH3), 4.05

(t, J = 6.4 Hz, 2H, -OCH2CH2-), 1.87-1.79 (m, 2H, -OCH2CH2CH2-), 1.52-1.45 (m, 2H, -

OCH2CH2CH2CH2-), 1.42 (t, J = 7.2 Hz, 3H, -OCH2CH3), 1.39-1.21 (m, 20H, -CH2-), 0.88 (t, J = 6.8 Hz,

3H, -O(CH2)13CH3). FT-IR (Nujol): 1713 cm-1 (C=O), 1284 cm-1 (C-O), 1255 cm-1 (CAr-O).

Compounds 5. General procedure. 12.9 mmol of the corresponding compound 4 is dissolved in ethanol

(150 mL), and 5.8 g (90 mmol) of KOH were added. The reaction mixture was heated to reflux, and

stirred overnight. Then, the mixture was cooled to room temperature. 0.5 L of water were added and the

mixture was subsequently acidified with 35% HCl until pH ≈ 2. The solid was filtered off and then it was

recrystallized from glacial acetic acid and washed with methanol. The product was a bright orange solid.

Yield = 92 %. TLC (silica gel, Hexanes/Ethyl acetate, 8:2) Rf = 0.30.

5a and 5b: 1H-RMN (400 MHz, CDCl3): δ 8.24 (d, J = 8.4 Hz, 2H, Ar-H), 7.96 (d, J = 8.4 Hz, 2H,

Ar-H), 7.93 (d, J = 8.8 Hz, 2H, Ar-H), 7.02 (d, J = 8.8 Hz, 2H, Ar-H), 4.09 (t, J = 6.8 Hz, 2H, -

OCH2CH2-), 1.92-1.82 (m, 1H, -CH-(CH3)2), 1.76-1.60 (m, 2H, -CH2CH2O-), 1.58-1.50 (m, 1H, -CH2-

CH(CH3)-CH2-), 1.38-1.24 (m, 3H, -CH2-), 1.22-1.11 (m, 3H, -CH2-), 0.96 (d, J = 6.8 Hz, 3H, -CH(CH3)-

), 0.87 (d, J = 6.8 Hz, 6H, -CH(CH3)2). FT-IR (Nujol): 3200-2300 cm-1 (COO-H), 1678 cm-1 (C=O), 1293

cm-1 (C-O), 1247 cm-1 (CAr-O).

5c: 1H-RMN (400 MHz, CDCl3): δ 8.24 (d, J = 8.8 Hz, 2H, Ar-H), 7.97 (d, J = 8.8 Hz, 2H, Ar-H),

7.94 (d, J = 8.8 Hz, 2H, Ar-H), 7.02 (d, J = 8.8 Hz, 2H, Ar-H), 4.09 (t, 6.6 Hz, 2H, -OCH2CH2-), 1.91-

1.78 (m, 2H, -OCH2CH2CH2-), 1.57-1.20 (m, 22H, -CH2-), 0.89 (t, J = 6.6 Hz, 3H, -O(CH2)13CH3). FT-

IR (Nujol): 3200-2300 cm-1 (COO-H), 1678 cm-1 (C=O), 1290 cm-1 (C-O), 1247 cm-1 (CAr-O).

Compounds 5’. 4.5 mmol of compounds 5 were dissolved in distilled dichloromethane under Argon

atmosphere. Then, 9.5 mmol of (COCl)2 were added via syringe and finally 3 drops of DMF. 2 hours later

the solution was evaporated until it was dry.

Compound 6. The synthesis of this compound was described in: J. Xu, E. R. Zubarev, Angew. Chem.

Int. Ed., 2004, 43, 5491.

Compounds 7. General procedure. 6.9 mmol of compound 6 were diluted with 100 mL of dry DCM.

Then, 9 mmol of TEA were added via syringe under argon atmosphere. Then, a solution of the

corresponding acid chloride 5’ in dry DCM was added drop wise. The reaction mixture was stirred for 15

hours at room temperature. Then, it was extracted with water and DCM. The organic layer was

evaporated, and the crude product was purified by column chromatography on silica gel (Hexane/Ethyl

acetate, 8:2). The first compound to be eluted, TLC (silica gel, Hexanes/Ethyl acetate, 8:2) Rf = 0.70, was

the disubstituted one, 8, and the second one, TLC (silica gel, Hexanes/Ethyl acetate, 8:2) Rf = 0.30, was

the monosubstituted one, 7. Yield: 26 % for 8 and 63 % for 7. They are red and viscous liquids.

7a and 7b: 1H-RMN (400 MHz, CDCl3): δ 8.32 (d, J = 8.4 Hz, 4H, Ar-H), 7.97 (d, J = 8.4 Hz, 4H,

Ar-H), 7.96 (d, J = 8.8 Hz, 4H, Ar-H), 7.50 (d, J = 2Hz, 2H, Ar-H central ring o-COOTIPS), 7.03 (d, J =

8.8 Hz, 4H, Ar-H), 7.48 (t, J = 2.0 Hz, 1H, Ar-H central ring p-COOTIPS), 4.10 (m, 4H, -OCH2CH2-),

1.92-1.83 (m, 2H, -CH-(CH3)2), 1.76-1.60 (m, 4H, -CH2CH2O-), 1.58-1.50 (m, 2H, -CH2-CH(CH3)-CH2-

), 1.41 (m, J = 7.6 Hz, 3H, -CH- TIPS), 1.38-1.24 (m, 6H, -CH2-), 1.22-1.11 (m, 6H, -CH2-), 1.14 (d, J =

7.6 Hz, 18H, -CH3 TIPS), 0.96 (d, J = 6.4 Hz, 6H, -CH(CH3)-), 0.88 (d, J = 6.8 Hz, 12H, -CH(CH3)2).

FT-IR (Nujol): 1739 cm-1 (C=O rings), 1703 cm-1 (C=O TIPS), 1250 cm-1 (CAr-O).

7c: 1H-RMN (400 MHz, CDCl3): δ 8.34 (d, J = 8.4 Hz, 4H, Ar-H), 7.98 (d, J = 8.4 Hz, 4H, Ar-H),

7.96 (d, J = 8.8 Hz, 4H, Ar-H), 7.87 (d, J = 2.0 Hz, 2H, Ar-H central ring o-COOTIPS), 7.02 (d, J = 8.8

Hz, 4H, Ar-H), 7.48 (d, J = 2.0 Hz, 1H, Ar-H central ring p-COOTIPS), 4.06 (t, J = 6.4 Hz, 4H, -

OCH2CH2-), 1.87-1.79 (m, 4H, -OCH2CH2CH2-), 1.52-1.43 (m, 4H, -OCH2CH2CH2-), 1.40-1.22 (m,

40H, -CH2-), 1.27 (t, J = 7.2 Hz, 3H, -CH- TIPS), 1.15 (d, J = 7.2 Hz, 18H, CH3 TIPS), 0.88 (t, J = 6.4

Hz, 6H, -O(CH2)11CH3). FT-IR (Nujol): 1737 cm-1 (C=O rings), 1703 cm-1 (C=O TIPS), 1250 cm-1 (CAr-

O).

Compounds 8. 1eq. of the corresponding triisopropyl protected compound, 8, was dissolved in

DCM and cooled to -78 ºC using iPrOH/ liquid N2. The solution was stirred for 5 min. and then 5 eq. of

TBAF (1.0 M solution in THF) was slowly added via syringe with rigorous stirring. Acetic acid was

added to the reaction mixture after 2 h. and the stirring proceeded for 5 min to ensure that all residual

TBAF was quenched before the mixture was allowed to warm to room temperature. The mixture was

diluted with DCM and washed with water. The organic layer was evaporated and the crude product was

purified by recrystallization in methanol or toluene. Yield = 70 %. Light orange solids. TLC (silica gel,

Hexanes/Ethyl acetate, 8:2) Rf = 0.15.

8a (A(S)10*) and 8b (A(R)10*): 1H-RMN (400 MHz, CDCl3): δ 8.34 (d, J = 8.4 Hz, 4H, Ar-H),

7.99 (d, J = 8.4 Hz, 4H, Ar-H), 7.95 (d, J = 8.8 Hz, 4H, Ar-H), 7.87 (d, J = 2.0 Hz, 2H, central ring p-

COOH), 7.55 (t, J = 2.0 Hz, 1H, central ring p-COOH), 7.03 (d, J = 8.8 Hz, 4H, Ar-H), 4.06 (t, J = 6.6

Hz, 4H, -OCH2CH2-), 1.92-1.83 (m, 2H, CH-(CH3)2), 1.76-1.60 (m, 4H, -CH2CH2O-), 1.58-1.50 (m, 2H,

-CH2-CH(CH3)-CH2), 1.38-1.24 (m, 6H, -CH2-), 1.22-1.11 (m, 6H, -CH2-), 0.94 (d, J = 6.4 Hz, 6H, -

CH(CH3)-), 0.85 (d, J = 6.8 Hz, 12H, -CH(CH3)2). FT-IR (KBr pellet): 3200-2300 cm-1 (COO-H), 1731

cm-1 (C=O ester), 1700 cm-1 (C=O acid), 1251 cm-1 (CAr-O). ME (FAB+): M+1 = 883.6. EA: calculated

C, 72.08; H, 7.08; N, 6.34; found 9aa: C, 72.02; H, 7.10; N, 6.28; found 9bb: C, 71, 66; H, 7.13; N, 6.31.

8c (A14): 1H-RMN (400 MHz, CDCl3): δ 8.34 (d, J = 8.4 Hz, 4H, Ar-H), 7.98 (d, J = 8.4 Hz, 4H,

Ar-H), 7.95 (d, J = 8.8 Hz, 4H, Ar-H), 7.87 (d, J = 2.0 Hz, 2H, Ar-H central ring o-COOH), 7.55 (t, J =

2.0 Hz, 1H, Ar-H central ring p-COOH), 7.02 (d, J = 8.8 Hz, 4H, Ar-H), 4.06 (t, J = 6.4 Hz, 4H, -

OCH2CH2-), 1.89-1.80 (m, 4H, -OCH2CH2CH2-), 1.52-1.44 (m, 4H, -OCH2CH2CH2-), 1.40-1.22 (m,

40H, -CH2-), 0.88 (t, J = 6.4 Hz, 3H, -O(CH2)13CH3). FT-IR (KBr pellet): 3200-2300 cm-1 (COO-H),

1734 cm-1 (C=O rings), 1698 cm-1 (C=O acid), 1248 cm-1 (CAr-O). ME (FAB+): M+1 = 995.7. EA:

calculated C, 73.61; H, 7.90; N, 5.63; found: C, 73.50; H, 7.95; N, 5.64.

Compound T. The synthesis of this compound was described in: J. Barberá, L. Puig, P. Romero,

J. L. Serrano, T. Sierra, J. Am. Chem. Soc., 2006, 128, 4487.

Preparation of hydrogen-bonded complexes: The complexes were obtained after evaporating a

THF solution of components T and 8 (An -A(S)10*, A(R)10* or A14-) in proportions 1:3, respectively,

by shaking at room temperature. The mixture, once heated to the isotropic state, was used for further

experiments.

Film processing and irradiation.

Thin films (about 300 nm) were prepared by casting solutions of the complexes in dichloromethane onto

clean quartz plates. The films were dried under vacuum for 24 h. The films were then heated above the

clearing temperature for 5 min and allowed to cool down room temperature.

The resulting films were irradiated for 30 minutes with the corresponding CPL from the 488 nm line of an

Ar+ laser, power 20 mW cm-2.

Characterization techniques NMR experiments were performed on a Bruker Avance 400 spectrometer, operating at frequency of

400.13 MHz for 1H and 100.61 MHz for 13C.. 1H NMR diffusion measurements were performed using stimulated echo sequence with bipolar gradient

pulses. Diffusion time (∆) was set within the interval 50-150 ms. The pulsed gradients were incremented

from 2 to 95% of the maximun strength in sixteen spaced steps with a duration (δ) of 2.6 to 4 ms. Data

were acquired in CD2Cl2 with sample rotation and the temperature was controlled at 298 K to minimize

convection effects.

Solid-state NMR experiments were performed using a double resonance (1H-X) probe with 4mm rotor

diameter, and the spinning frequency was set to 10 kHz. Data were acquired at 296K and chemical shifts

are referenced to TMS. The 1H and 13C 90º pulse length were of 5.1 and 4.7 μs respectively and the CP

contact time of 1.5 ms. The recycle delay was 5s. The pulse sequence employed consisted of ramped

cross-polarisation with TPPM decoupling.

Infrared spectra for all the complexes were obtained by using a Mattson Genesis II FTIR

spectrophotometer in the 400-4000 cm-1 spectral range.

The textures of the mesophases were studied with an optical microscope (Nikon) with crossed polarizers

and connected to a Mettler FP82 hot stage and a Mettler FP90 central processor. Measurements of the

transition temperatures were made using a TA instrument 2000 differential scanning calorimeter with a

heating or cooling rate of 10ºC/min. The apparatus was calibrated with indium (156.6 ºC, 28.44 J/g) and

tin (232.1 ºC, 60.5 J/g).

X-ray diffraction studies were carried out at room temperature using a Pinhole camera (Anton-Paar)

operating with a point focused Ni-filtered Cu Kα beam. The sample was held in Limdemann glass

capillaries (1 mm diameter) and heated, when necessary, with a variable-temperature attachment. The

diffraction patterns were collected on a flat photographic film perpendicular to the x-ray beam.

CD spectra were recorded in a Jasco J-810. Neat samples were prepared by casting a solution of the

material onto a quartz plate and subsuquent melting above the clearing point. As heating stage, a Mettler

FP82, with a central processor Mettler FP80, was used conveniently modified to fix within the sample

holder of the CD spectrometer. Solution experiments were carried out in dichloromethane at room

temperature.

1H NMR (CD2Cl2)

FIGURE SI1. Significant field shift was observed for proton signals involved in complexation (Ha, Hb, Hc). Protons near the complexating groups (eg. -N-CH2-) experimented down-field shift upon complexation

N

N

N

NNHH

H H

H C12H25

Ha Hb

Hc

T

T-A10*

A10*

Hc

Ha Hb

-N-CH2-

13C NMR (CD2Cl2)

FIGURE SI2. Carbon atoms of the central benzene ring show significant shift in the complex.

Carbon atoms of the N-alkyl tail (Cn), sandwiched between azobenzene groups, show up-field shift in the complex

CbCa

Ca Cb

OO

OO

O OH

NN

NN

N

N

H

H

HH

H

O

O O

NN

O

O

O

O HO

OH

OO

O

NN

O

O

O OH

C

Cn

T

T-A10*

A10*

DOSY experiments

FIGURE SI3. Since there is fast exchange between the complex and components in the NMR

timescale the DOSY experiments provide an “apparent diffusion coefficient” (D) for the complex. It is important to point up that no proton signal shows the D coefficient of the isolated triazine, what can be accounted for by the fact that acid and triazine diffuse within the same entity.

T T-A(S)10* [1:3]

-logD

POM and DSC

Figure SI4. POM microphotograph (sample prepared between two glasses) and DSC cooling scan

of complex T-A(S)10*.

Figure SI5. POM microphotographs (sample prepared between two glasses) and DSC cooling scan

of complex T-A14

-0.8

-0.6

-0.4

-0.2

20 40 60 80 100 120 140 160 180 ºC Exo Down

Colh

I

(W/g)

(W/g)

-1.4

-1.2

-1.0

-0.8

-0.6

20 40 60 80 100 120 140 160 ºC

Exo Down

Colr

I

X-ray Diffraction Table SI1. X-ray diffraction data for the mesophases of the complexes.

Complex T(ºC) Phase Parameters area(Å2) dobs(Å) dcalc(Å) hk

T-A(S)10* t.a. Colh a = 65.2 3684 56.4 56.5 10

h = 3.3 32.9 32.6 11

21.3 21.3 21

16.2 16.3 31

T-A(R)10* t.a. Colh a = 66.0 3775 56.9 57.2 10

h = 3.3 33.0 33.0 11

21.8 21.6 21

16.8 16.5 31

T-A14 t.a. Colr a = 75 5325 51.3 51.6 11

b = 71 35.6 35.5 02

32.2 32.1 12

26.1 25.8 22

21.8 23.6 31

Density calculations: The relationship between the density ρ of the complexes and the number Z

of tetrameric complexes in the unit cell is given by the following equation: ρ = (M / N) / (V / Z) where M

is the molar mass (in g) of each 1:3 complex, N the Avogadro number, and V the unit cell volume (in

cm3). V is calculated by the formula V = (√3/2)a2h x 10-24 for a hexagonal lattice and V = abh x 10-24 for a

orthorhombic lattice, where a, b, h are the lattice constants in Å.

Additional comment: The possibility of the hexagonal columnar mesophase of the chiral

complexes being actually rectangular, whose parameters incidentally coincide with those expected for a

hexagonal lattice, has been considered. However in these “pseudohexagonal” rectangular columnar

mesophases found for some chiral compounds# one or two additional diffraction maxima are always

observed which are not consistent with the hexagonal symmetry. Therefore this possibility was ruled out

on the basis of the X-ray diffraction data. Moreover the hexagonal symmetry of the mesophase is

demonstrated by the occurrence of four X-ray reflections, all of which are consistent with a 2D hexagonal

lattice. # References: J. Barberá, R. Iglesias, J.L. Serrano, T. Sierra, M.R. de la Fuente, B. Palacios, M.A. Pérez-Jubindo, J.

Am. Chem. Soc. 1998, 120, 2908; J. Barberá, E. Cavero, M. Lehmann, J.L. Serrano, T. Sierra, J.T. Vázquez, J. Am. Chem. Soc.

2003, 125, 4527.

FIGURE SI6. Small angle (SAXS) and wide angle (WAXS) x-ray scattering patterns of the mesophase of complex T-A(S)10* taken at room temperature after cooling from the isotropic liquid. a is the lattice parameter of the hexagonal arrangement and h stands for the average stacking distance. Two columns per lattice node could indicate a double helix organization.

FIGURE SI7

SAXS and WAXS diagrams of the mesophase of complex T-A14 taken at room temperature after cooling from the isotropic liquid. a and b are the lattice parameters of the rectangular arrangement. Two columns per lattice node could indicate a double helix organization.

(10)

(31)

(11)

SAXS pattern

a=65.2 Å

Diffuse haloh=3.3 Å

WAXS pattern

ColhT-A(S)10*

Z = 2 :Two columns in each lattice node:

Double helix?

(21)

Z =4 :Two columnsin each lattice node:

ColrT-A14

b=71 Å

a=75 Å

SAXS pattern Diffuse halo

Double helix?

WAXS pattern(22)

(02)

(11)

(12)

(31) SAXS pattern

CD Measurements.

FIGURE SI8. CD (above) and UV (below) spectra of the enantiomeric complexes. Red (T-

(R)A10*) and black (T-(S)A10*) lines in the CD plot correspond to thin films on quartz plates.

T-(R)A10* (rt)

300 350 400 450 500 550 6000.00

0.25

0.50

0.75

1.00

1.25

1.50

Abso

rban

ce

W avelength (nm )

300 400 500 600-600 -400 -200

0 200 400 600

Ellip

ticity

Wavelength

CD

UV

T-(S)A10* (rt)