Supporting Information

© Wiley-VCH 2008

69451 Weinheim, Germany

S1

Supporting Information

Liquid crystal engineering with anchor-shaped molecules: Honeycombs

with hexagonal and trigonal symmetries formed by polyphilic bent-core

molecules Benjamin Glettner, Feng Liu, Xiangbing Zeng, Marko Prehm, Ute Baumeister, Goran Ungar,* and Carsten

Tschierske*

Dipl.-Chem. B. Glettner, Prof. Dr. C. Tschierske

Institute of Chemistry, Organic Chemistry

Martin-Luther-University Halle-Wittenberg

Kurt-Mothes-Str. 2, D-06120 Halle (Germany)

Fax: (+49) 345-55-27346

E-mail: carsten.tschierske@chemie.uni-halle.de

Dr. M. Prehm, Dr. U. Baumeister,

Institute of Chemistry, Physical Chemistry,

Martin-Luther-University Halle-Wittenberg,

Mühlpforte 1, D-06108 Halle (Germany)

F. Liu, Dr. X. B. Zeng, Prof. G. Ungar

Department of Engineering Materials

University of Sheffield

Robert Hadfield Building Mappin Street,

Sheffield S1 3JD (Great Britain)

Fax: (+44) 114-222-5943

E-mail: g.ungar@sheffield.ac.uk

S2

.

S3

2. Details of X-ray scattering experiments and data analysis 2.1 X-ray scattering of powder-like and aligned samples X-ray investigations of powder-like samples were carried out with a Guinier film camera (Huber), samples in glass capillaries (∅ 1 mm) in a temperature-controlled heating stage, quartz-monochromatized CuKα radiation, 30 to 60 min exposure time, calibration with the powder pattern of Pb(NO3)2. Aligned samples were obtained on a glass plate. Alignment was achieved upon slow cooling (rate: 1 – 0.01 K⋅min–1) of a small droplet of the sample and takes place at the sample–glass or at the sample–air interface, with domains fiber-like disordered around an axis perpendicular to the interface. The aligned samples were held on a temperature-controlled heating stage and the diffraction patterns were recorded with a 2D detector (HI-STAR, Siemens). 2.2 Synchrotron X-ray diffraction experiments High-resolution small-angle powder diffraction experiments were recorded on Beamline I22 of the Diamond Light Source, UK. Samples were held in evacuated 1 mm capillaries. A modified Linkam hot stage was used, with a hole for the capillary drilled through the silver heating block and mica windows attached to it on each side. A Rapid II area detector was used. q calibration and linearization were verified using several orders of layer reflections from silver behemate and a series of n-alkanes. 2.3 Data from synchrotron experiments Tables S1 – S4 contain the following information on individual small-angle Bragg reflections for the LC phases of compounds 1c, 2a, 2b and 2c: dobs = observed spacing, dcalc = calculated spacing, I = observed intensity (Lorentz and multiplicity corrected), φ = phase angle used in electron density calculation. Table S1. SAXS data for the Colhex/p6mm phase of compound 1c at T = 127 °C.

(hk) dobs (nm) dcalc (nm) I φ (deg)

(10) 3.79 3.79 100.0 0

(11) 2.20 2.19 7.1 0

(20) 1.89 1.89 4.6 0

(21) 1.44 1.43 22.1 180

(30) 1.27 1.26 4.1 180

(22) 1.10 1.09 7.0 0

a = 4.37 nm

S4

Table S2. SAXS data for the Colhex/p3m1 phase of compound 2a at 80 °C.

(hk) dobs. (nm) dcalc. (nm) I φ (deg)

(10) 2.45 2.45 100.0 198.6

(20) 1.22 1.22 1.7 -16.9

(21) 9.3 9.2 2.3 14.3

a = 2.82 nm

Table S3. SAXS data for the Colhex/p3m1 phase of compound 2b at 100 °C.

(hk) dobs. (nm) dcalc. (nm) I φ (deg)

(10) 2.49 2.49 100.0 -4.1

(11) 1.44 1.44 3.5 0

(20) 1.25 1.25 0.7 -3.6

(21) 9.5 9.4 2.0 173.7

a = 2.88 nm

Table S4. SAXS data for the Colhex/p6mm phase of compound 2c at 120 °C.

(hk) dobs. (nm) dcalc. (nm) I φ (deg)

(10) 4.43 4.43 100.0 0

(11) 2.56 2.56 0.5 0

(20) 2.22 2.22 5.1 0

(21) 1.68 1.68 27.2 180

(22) 1.29 1.28 1.9 0

(40) 1.11 1.11 4.1 0

a = 5.12 nm

S5

2.4 Calculation of the number of molecules in the cell and cell wall

Table S5. Parameters of the Colhex phases of compounds 1 and 2. a

Comp.

ahex/nm

Acell/nm2

Vmol/nm3

Vcell/nm3

ncell,cryst

ncell,liqu

ncell,av

nwall

1c 4.37 16.54 1.11 7.44 6.7 5.3 6.0 2.0

2a 2.82 6.89 0.89 3.10 3.5 2.7 3.1 2.1

2b 2.88 7.18 0.92 3.23 3.5 2.8 3.1 2.1

2c 5.12 22.70 1.17 10.22 8.7 6.8 7.8 2.6 a Vcell = volume of the unit cell defined by the a2sin(60°) x 0.45 nm; Vmol = volume for a single molecule as calculated using the crystal volume increments;S1 ncell,cryst = number of molecules in the unit cell, calculated according to ncell = Vcell/Vmol (average packing coefficient in the crystal is k = 0.7;S2 ncell,liqu = number of molecules in the unit cell of an isotropic liquid with an average packing coefficient k = 0.55, calculated according to ncell,liqu = 0.55/0.7 x ncell,cryst; ncell,av = number of molecules in the unit cell in the LC phase estimated as the average of that in the ncell,cryst and ncell,liqu; nwall = number of molecules in the cross section of the cylinder walls as calculated from ncell,av. 2.5 Reconstruction of electron density maps and model calculations

Fourier reconstruction of the electron density was carried out using the general formula for 2-d periodic systems: ρ(xy) = Σhk F(hk) exp[2πi(hx+ky)] = Σhk )(hkI exp[2πi(hx+ky) + iφ(hk)] Specific formulae for the hexagonal plane groups can be found in International Tables of Crystallography. The phase choice for the p6mm phase, with φ limited to 0 or 180° was relatively straightforward on grounds of physical viability. For the noncentrosymmetric p3m1 phase, geometrical electron density distribution models were constructed (Figure 2a,e) with fixed relative densities and areas based on the data calculated from molecular models, as given in Table S6. Structure factors were calculated analytically. Intensities and phases thus obtained are given in Table 7a,b, together with the observed intensities, for comparison. ρ(xy) maps based on the calculated phases were then reconstructed using calculated intensities (see Figure 2b,f) and observed intensities (see Figure 2c,g).

S6

Table S6. Electron densities and volume fractions of the four incompatible segments of molecules 2a and 2b used in the trigonal scattering models (Figures 2a and 2e of main text).a

V% Electron Density

(a.u.) 2a 2b

diol group 0.52 25.3 24.1

aromatic core 0.48 42.2 40.4

alkyl segment 0.40 32.5 10.5

perfluoro segment 0.80 25.0 a Calculation was performed using Material Studio by Accelrys.

Table S7a. Structure factor phase angles and diffraction intensities calculated from the scattering model of the Colhex/p3m1 phase of compound 2a in Figure 2a, together with the experimental intensities. The intensities are scaled to I10 = 100.

(hk) Phase (deg.) Calculated

Intensity Experimental

Intensity (10) 198.6 100.0 100.0

(11) 180.0 6.5 /

(20) –16.9 1.3 1.7

(21) 14.3 5.7 2.3

(30) 15.1 0.9 /

Table S7b. Structure factor phase angles and diffraction intensities calculated from the scattering model of the Colhex/p3m1 phase of compound 2b in Figure 2e, together with the experimental intensities. The intensities are scaled to I10 = 100.

(hk) Phase (deg.) Calculated Intensity

Experimental Intensity

(10) -4.1 100.0 100.0

(11) 0.0 5.6 3.5

(20) -3.6 0.5 0.7

(21) 173.7 4.8 2.0

S7

3. Molecular dynamics simulation Annealing dynamics runs were carried out using the Universal Force Field (Material Studio, Accelrys). The structure in Figure 1d, 2d and 2h was obtained with six or three molecules in a rhombic prism box with the side equal to the unit cell length and a height of 0.45 nm, with 3-d periodic boundary conditions. 30 temperature cycles of NVT dynamics were run between 300 and 500 K, with a total annealing time of 30 ps.

4. Syntheses and analytical data

4.1 Intermediates 2,6-Dibromophenol:S3 A solution of 18.6 ml (0.36 mol) bromine in 100 ml glacial acetic acid is added dropwise to an ice-cold solution of 25.0 g (0.18 mol) 4-hydroxybenzoic acid in a mixture of 100 ml glacial acetic acid and 100 ml half-concentrated sulphuric acid. The reaction mixture is stirred overnight. The resulting precipitate is filtered and the solution is diluted with water creating a further amount of precipitate which is also filtered. The crude 3,5-dibromo-4-hydroxybenzoic acid is heated with 100 ml water for five hours in the autoclave at 190-200 °C (oil bath temperature). After cooling, the mixture is extracted three times with Et2O. The combined organic phases are washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: CHCl3) and crystallized from n-pentane. Yield: 33.4 g (0.133 mol; 73 %); white crystalline solid; mp. 52-55 °C (lit. 56-57 °C); 1H-NMR (400 MHz, CDCl3): δ = 5.86 (s, 1H, OH); 6.68 (t, 3J(H,H) = 8.1 Hz, 1H, ArH); 7.43 ppm (d, 3J(H,H) = 8.1 Hz, 2H, ArH). 7,7,8,8,9,9,10,10,10-Nonafluorodecanol:S4 Under an argon atmosphere a mixture of 7.6 g (22 mmol) perfluorobutyl iodide, 2.2 g (22 mmol) 5-hexene-1-ol, 0.25 g (1 mol-%) Pd(PPh3)4 and 100 ml dry n-hexane is stirred for two weeks at room temperature. The reaction mixture is then filtered and evaporated under reduced pressure. The crude product is used for the next step without further purification. A solution of the crude product in 50 ml dry Et2O is added dropwise to a suspension of 1.1 g (29 mmol) LiAlH4 in 50 ml dry Et2O. The reaction mixture is stirred under reflux for ten hours. The mixture is then hydrolised carefully with diluted hydrochloric acid. The organic phase is separated and the water phase is extracted two times with Et2O. The combined organic phases are washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: CHCl3 with 2% (V/V) MeOH). Yield: 2.52 g (7.9 mmol; 36 %); yellowish liquid; 1H-NMR (400 MHz, CDCl3): δ = 1.38-1.64 (m, 8H, (CH2)4); 2.06 (m, 2H, CH2CF2); 3.63 ppm (t, 3J(H,H) = 6.5 Hz, 2H, OCH2). 5,5,6,6,7,7,8,8,9,9,10,10,10-Tridecafluorodecanol: Yield: 4.4 g (11.2 mmol; 50 %); yellowish liquid; 1H-NMR (400 MHz, CDCl3): δ = 1.60-1.74 (m, 4H, (CH2)2); 2.09 (m, 2H, CH2CF2); 3.67 ppm (t, 3J(H,H) = 6.0 Hz, 2H, OCH2). 7,7,8,8,9,9,10,10,10-Nonafluorodecylbromide: A mixture of 2.52 g (7.9 mmol) 7,7,8,8,9,9,10,10,10-nonafluorodecanol, 20 ml concentrated hydrobromic acid, 4 ml concentrated sulphuric acid, 0.25 g tetrabutylammonium hydrogensulphate and 20 ml benzene is stirred for 10 hours under reflux. Water is then added carefully and the mixture is extracted three times with Et2O. The combined organic phases are washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude product is purified by column

S8

chromatography on silica gel (eluent: CH2Cl2). Yield: 3.0 g (7.8 mmol; 99 %); colorless liquid; 1H-NMR (400 MHz, CDCl3): δ = 1.38-1.51 (m, 4H, (CH2)2); 1.61 (quin, 3J(H,H) = 7.7 Hz, 2H, CH2); 1.86 (quin, 3J(H,H) = 7.1 Hz, 2H, CH2); 2.05 (m, 2H, CH2CF2); 3.40 ppm (t, 3J(H,H) = 6.7 Hz, 2H, BrCH2). 5,5,6,6,7,7,8,8,9,9,10,10,10-Tridecafluorodecylbromide: Purified by column chromato-graphy on silica gel (eluent: CH2Cl2). Yield: 3.3 g (7.3 mmol; 65 %); colorless liquid; 1H-NMR (400 MHz, CDCl3): δ = 1.78 (m, 2H, CH2); 1.95 (m, 2H, CH2); 2.09 (m, 2H, CH2CF2); 3.41 ppm (t, 3J(H,H) = 6.5 Hz, 2H, BrCH2). 2,6-Dibromo(7,7,8,8,9,9,10,10,10-nonafluorodeyloxy)benzene: A mixture of 100 mg (0.4 mmol) 2,6-dibromophenol, 153 mg (0.4 mmol) 7,7,8,8,9,9,10,10,10-nonafluoro-decylbromide, 0.5 g (3.6 mmol) K2CO3 and 20 ml MeCN is stirred for 20 hours under reflux. Water is then added and the mixture is extracted three times with Et2O. The combined organic phases are washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: CHCl3). Yield: 185 mg (0.33 mmol; 84 %); colorless oil; 1H-NMR (400 MHz, CDCl3): δ = 1.34-1.46 (m, 4H, (CH2)2); 1.62 (quin, 3J(H,H) = 7.6 Hz, 2H, OCH2CH2CH2); 1.86 (quin, 3J(H,H) = 7.1 Hz, 2H, OCH2CH2); 2.05 (m, 2H, CH2CF2); 3.99 (t, 3J(H,H) = 6.4 Hz, 2H, OCH2); 6.83 (t, 3J(H,H) = 8.0 Hz, 1H, ArH); 7.48 ppm (d, 3J(H,H) = 7.9 Hz, 2H, ArH). 2,6-Dibromo(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyloxy)benzene: Purified by column chromatography on silica gel (eluent: CHCl3). Yield: 0.4 g (0.64 mmol; 94 %); colorless oil; 1H-NMR (400 MHz, CDCl3): δ = 1.92-1.97 (m, 4H, (CH2)2); 2.21 (m, 2H, CH2CF2); 4.03 (t, 3J(H,H) = 5.6 Hz, 2H, OCH2); 6.84 (t, 3J(H,H) = 8.0 Hz, 1H, ArH); 7.48 ppm (d, 3J(H,H) = 7.9 Hz, 2H, ArH). 2,6-Dibromo(12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoronona-decyloxy)benzene: Purified by column chromatography on silica gel (eluent: CHCl3). Yield: 0.42 g (0.51 mmol; 86 %); colorless oil; 1H-NMR (400 MHz, CDCl3): δ = 1.24-1.62 (m, 16H, (CH2)8); 1.85 (quin, 3J(H,H) = 7.1 Hz, 2H, OCH2CH2); 2.03 (m, 2H, CH2CF2); 3.98 (t, 3J(H,H) = 6.5 Hz, 2H, OCH2); 6.82 (t, 3J(H,H) = 8.0 Hz, 1H, ArH); 7.47 ppm (d, 3J(H,H) = 7.9 Hz, 2H, ArH). 2,6-Dibromododecyloxybenzene: Purified by column chromatography on silica gel (eluent: CHCl3). Yield: 410 mg (0.98 mmol; 98 %); colorless oil; 1H-NMR (400 MHz, CDCl3): δ = 0.87 (t, 3J(H,H) = 6.8 Hz, 3H, CH3); 1.24-1.36 (m, 16H, (CH2)8); 1.51 (quin, 3J(H,H) = 7.9 Hz, 2H, OCH2CH2CH2); 1.86 (quin, 3J(H,H) = 7.3 Hz, 2H, OCH2CH2); 3.98 (t, 3J(H,H) = 6.6 Hz, 2H, OCH2); 6.82 (t, 3J(H,H) = 8.0 Hz, 1H, ArH); 7.47 ppm (d, 3J(H,H) = 8.1 Hz, 2H, ArH). 4-[(2,2-Dimethyl-1,3-dioxolane-4-yl)methoxy]phenylethynyltrimethylsilane: Under an argon atmosphere a mixture of 12.5 g (43.5 mmol) 4-(4-bromophenyloxymethyl)-2,2-dimethyl-1,3-dioxolane,S5 5.3 g (54.4 mmol) ethynyltrimethylsilane, 1.5 g (3 mol-%) Pd(PPh3)4, 0.17 g (2 mol-%) copper(I) iodide and 50 ml dry Et3N is stirred under reflux for five hours. The reaction mixture is evaporated under reduced pressure and the residue is taken up in Et2O and water. The organic layer is separated and the water phase is extracted two times with Et2O. The combined organic phases are washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude product is crystallized from MeOH. Yield: 10.12 g (33.2 mmol; 76 %); colorless crystals; mp. 46-48 °C; 1H-NMR (400 MHz, CDCl3): δ = 0.22 (s, 9H, Si(CH3)3); 1.38 (s, 3H, CH3); 1.44 (s, 3H, CH3); 3.85-4.16 (m, 4H, OCH2); 4.44

S9

(quin, 3J(H,H) = 5.9 Hz, 1H, OCH); 6.81 (d, 3J(H,H) = 8.9 Hz, 2H, ArH); 7.37 ppm (d, 3J(H,H) = 8.9 Hz, 2H, ArH). 4-[(2,2-Dimethyl-1,3-dioxolane-4-yl)methoxy]phenylacetylene: 10.1 g (33.2 mmol) of 4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]phenylethynyltrimethylsilane are treated with a solution of 2.0 g KOH in 100 ml MeOH and stirred for three hours at room temperature. The reaction mixture is evaporated under reduced pressure and the residue is taken up in Et2O and water. The organic layer is separated and the water phase is extracted two times with Et2O. The combined organic phases are washed with brine, dried over Na2SO4 and evaporated under reduced pressure. The crude product is crystallized from MeOH. Yield: 6.2 g (26.7 mmol; 80 %); colorless crystals; mp. 39-41 °C; 1H-NMR (400 MHz, CDCl3): δ = 1.38 (s, 3H, CH3); 1.44 (s, 3H, CH3); 2.98 (s, 1H, C≡CH); 3.86-4.16 (m, 4H, OCH2); 4.45 (quin, 3J(H,H) = 5.9 Hz, 1H, OCH); 6.83 (d, 3J(H,H) = 8.9 Hz, 2H, ArH); 7.40 ppm (d, 3J(H,H) = 8.7 Hz, 2H, ArH). 4.2 Acetonide protected bolaamphiphiles 4,4’’-Bis[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]-2’-(7,7,8,8,9,9,10,10,10-nonafluoro-decyloxy)-m-terphenyl: Under an argon atmosphere a mixture of 185 mg (0.33 mmol) 2,6-dibromo(7,7,8,8,9,9,10,10,10-nonafluorodeyloxybenzene, 0.21 g (0.83 mmol) 4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]benzene boronic acid,S6 40 mg (5 mol-%) Pd(PPh3)4, 40 ml glyme and 20 ml of saturated solution of NaHCO3 is stirred for six hours under reflux. After cooling, the organic layer is separated and the water phase is extracted two times with CHCl3. The combined organic phases are dried over Na2SO4 and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: CHCl3). Yield: 0.23 g (0.28 mmol; 85 %); yellow oil; 1H-NMR (400 MHz, CDCl3): δ = 1.28-1.38 (m, 6H, (CH2)3); 1.40 (s, 6H, CH3); 1.46 (s, 6H, CH3); 1.59 (m, 2H, OCH2CH2); 2.02 (m, 2H, CH2CF2); 3.17 (t, 3J(H,H) = 6.3 Hz, 2H, OCH2); 3.87-4.19 (m, 8H, OCH2); 4.49 (quin, 3J(H,H) = 5.9 Hz, 2H, OCH); 6.94 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.18 (t, 3J(H,H) = 7.5 Hz, 1H, ArH); 7.25 (d, 3J(H,H) = 8.3 Hz, 2H, ArH); 7.52 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH). 4,4’’-Bis[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]-2’-(5,5,6,6,7,7,8,8,9,9,10,10,10-tri-decafluorodecyloxy)-m-terphenyl: Purified by column chromatography on silica gel (eluent: CHCl3). Yield: 0.22 g (0.25 mmol; 78 %); yellow oil; 1H-NMR (400 MHz, CDCl3): δ = 1.21-1.33 (m, 4H, (CH2)2); 1.40 (s, 6H, CH3); 1.46 (s, 6H, CH3); 1.96 (m, 2H, CH2CF2); 3.19 (t, 3J(H,H) = 6.2 Hz, 2H, OCH2); 3.87-4.19 (m, 8H, OCH2); 4.49 (quin, 3J(H,H) = 5.9 Hz, 2H, OCH); 6.94 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.18 (t, 3J(H,H) = 7.5 Hz, 1H, ArH); 7.25 (d, 3J(H,H) = 8.3 Hz, 2H, ArH); 7.52 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH). 4,4’’-Bis[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]-2’-(12,12,13,13,14,14,15,15,16,16,-17,17,18,18,19,19,19-heptadecafluorononadecyloxy)-m-terphenyl: Purified by column chromatography on silica gel (eluent: CHCl3). Yield: 0.36 g (0.334 mmol; 95 %); yellowish solid; 1H-NMR (400 MHz, CDCl3): δ = 1.13-1.57 (m, 18H, (CH2)9); 1.40 (s, 6H, CH3); 1.46 (s, 6H, CH3); 2.03 (m, 2H, CH2CF2); 3.17 (t, 3J(H,H) = 6.4 Hz, 2H, OCH2); 3.87-4.19 (m, 8H, OCH2); 4.49 (quin, 3J(H,H) = 5.9 Hz, 2H, OCH); 6.94 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.18 (t, 3J(H,H) = 7.5 Hz, 1H, ArH); 7.25 (d, 3J(H,H) = 8.3 Hz, 2H, ArH); 7.52 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH). 1,3-Bis{4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]phenylethynyl}-2-(5,5,6,6,7,7,8,8,-9,9,10,10,10-tridecafluorodecyloxy)benzene: Under an argon atmosphere a mixture of 400 mg (0.64 mmol) 2,6-dibromo(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyloxy)benzene,

S10

325 g (1.40 mmol) 4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]phenylacetylene, 42 mg (3 mol-%) Pd(PPh3)4, 5 mg (2 mol-%) copper(I) iodide and 30 ml dry triethylamine is stirred under reflux for five hours. The reaction mixture is evaporated under reduced pressure and the residue is taken up in diethyl ether and water. The organic layer is separated and the water phase is extracted two times with diethyl ether. The combined organic phases are washed with a saturated solution of sodium chloride, dried over sodium sulphate and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: n-hexane with 50 % (V/V) EtOAc). Yield: 0.36 g (0.39 mmol; 61 %); white solid; 1H-NMR (400 MHz, CDCl3): δ = 1.39 (s, 6H, CH3); 1.45 (s, 6H, CH3); 1.93-1.94 (m, 4H, (CH2)2CH2CF2); 2.12 (m, 2H, CH2CF2); 3.87-4.18 (m, 8H, OCH2); 4.31 (t, 3J(H,H) = 5.2 Hz, 2H, OCH2CH2); 4.47 (quin, 3J(H,H) = 5.9 Hz, 2H, OCH); 6.87 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.03 (t, 3J(H,H) = 7.7 Hz, 1H, ArH); 7.42 (d, 3J(H,H) = 7.7 Hz, 2H, ArH); 7.43 ppm (d, 3J(H,H) = 8.9 Hz, 4H, ArH). 1,3-Bis{4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]phenylethynyl}-2-(12,12,13,13,14,-14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluorononadecyloxy)benzene: Purified by column chromatography on silica gel (eluent: Et2O). Yield: 0.13 g (0.12 mmol; 40 %); colorless solid; 1H-NMR (400 MHz, CDCl3): δ = 1.19-1.33 (m, 12H, (CH2)6); 1.39 (s, 6H, CH3); 1.45 (s, 6H, CH3); 1.52-1.59 (m, 4H, OCH2CH2CH2, CH2CH2CF2); 1.86 (quin, 3J(H,H) = 7.1 Hz, 2H, OCH2CH2); 2.02 (m, 2H, CH2CF2); 3.87-4.17 (m, 8H, OCH2); 4.29 (t, 3J(H,H) = 6.4 Hz, 2H, OCH2CH2); 4.46 (quin, 3J(H,H) = 5.9 Hz, 2H, OCH); 6.87 (d, 3J(H,H) = 8.7 Hz, 4H, ArH); 7.00 (t, 3J(H,H) = 7.7 Hz, 1H, ArH); 7.40 (d, 3J(H,H) = 7.7 Hz, 2H, ArH); 7.44 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH). 1,3-Bis{4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]phenylethynyl}-2-dodecyloxy-benzene: Purified by column chromatography on silica gel (eluent: CH2Cl2 with 10% (V/V) Et2O). Yield: 0.3 g (0.41 mmol; 41 %); colorless oil; 1H-NMR (400 MHz, CDCl3): δ = 0.86 (t, 3J(H,H) = 7.0 Hz, 3H, CH3); 1.20-1.33 (m, 16H, (CH2)8); 1.39 (s, 6H, CH3); 1.45 (s, 6H, CH3); 1.55 (m, 2H, OCH2CH2CH2); 1.86 (m, 2H, OCH2CH2); 3.87-4.17 (m, 8H, OCH2); 4.28 (t, 3J(H,H) = 6.4 Hz, 2H, OCH2C11H23); 4.46 (quin, 3J(H,H) = 5.9 Hz, 2H, OCH); 6.87 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.00 (t, 3J(H,H) = 7.7 Hz, 1H, ArH); 7.40 (d, 3J(H,H) = 7.7 Hz, 2H, ArH); 7.44 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH). 4.3 Compounds 1 4,4’’-Bis(2,3-dihydroxypropyloxy)-2’-(7,7,8,8,9,9,10,10,10-nonafluorodecyloxy)-m-terphenyl (1a): A mixture of 0.23 g (0.28 mmol) 4,4’’-bis[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]-2’-(7,7,8,8,9,9,10,10,10-nonafluorodecyloxy)-m-terphenyl, 40 ml MeOH and 0.5 ml concentrated hydrochloric acid is stirred for two hours at room temperature. The reaction mixture is then evaporated under reduced pressure and the residue is purified by column chromatography on silica gel (eluent: CHCl3 with 6 % (V/V) MeOH). The crude product is crystallized from CH2Cl2/n-pentane. Yield: 95 mg (0.13 mmol; 46 %); white solid; 1H-NMR (400 MHz, CDCl3): δ = 0.98-1.57 (m, 8H, (CH2)4); 1.95 (m, 2H, CH2CF2); 3.18 (t, 3J(H,H) = 6.0 Hz, 2H, OCH2); 3.78-4.12 (m, 10H, OCH2, OCH); 6.95 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.17 (t, 3J(H,H) = 7.5 Hz, 1H, ArH); 7.26 (d, 3J(H,H) = 7.9 Hz, 2H, ArH); 7.53 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH); 13C-NMR (100 MHz, CDCl3): δ = 20.08, 25.58, 28.73, 29.68, 30.82 (CH2); 63.80, 63.80, 69.39, 69.39 (OCH2); 70.52, 70.52 (OCH); 72.61 (OCH2); 114.11, 114.11, 114.11, 114.11, 124.12, 129.76, 129.76, 130.68, 130.68, 130.68, 130.68, 131.94, 131.94, 135.48, 135.48, 153.93, 157.61, 157.61 ppm; 19F-NMR (200 MHz, CDCl3): δ = -81.46 (t, 3J(H,H) = 9.3 Hz, 3F, CF3); -114.96 (m, 2F, CF2CH2); -124.86 (s, 2F, CF2); -

S11

126.42 ppm (s, 2F, CF2); elemental analysis: C34H37F9O7 requires: C 56.04, H 5.12, N 0.00 %; found: C 56.28, H 5.34, N 0.00 %. 4,4’’-Bis(2,3-dihydroxypropyloxy)-2’-(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyloxy)-m-terphenyl (1b): Crystallized from CH2Cl2/n-pentane. Yield: 42 mg (0.052 mmol; 21 %); colorless solid; 1H-NMR (400 MHz, CDCl3): δ = 1.21-1.33 (m, 4H, (CH2)2); 1.74 (m, 2H, CH2CF2); 3.20 (t, 3J(H,H) = 5.5 Hz, 2H, OCH2); 3.74-4.12 (m, 10H, OCH2, OCH); 6.95 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.19 (t, 3J(H,H) = 7.6 Hz, 1H, ArH); 7.26 (d, 3J(H,H) = 7.1 Hz, 2H, ArH); 7.52 ppm (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 19F-NMR (200 MHz, CDCl3): δ = -81.20 (t, 3J(H,H) = 9.9 Hz, 3F, CF3); -114.88 (m, 2F, CF2CH2); -122.33 (s, 2F, CF2); -123.27 (s, 2F, CF2); -124.00 (s, 2F, CF2); -126.49 ppm (s, 2F, CF2); elemental analysis: C34H33F13O7 (0.7 H2O) requires: C 50.22, H 4.26, N 0.00 %; found: C 50.16, H 4.46, N 0.00 %. 4,4’’-Bis(2,3-dihydroxypropyloxy)-2’-(12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluorononadecyloxy)-m-terphenyl (1c): Crystallized from MeOH. Yield: 129 mg (0.13 mmol; 42 %); colorless crystals; 1H-NMR (400 MHz, CDCl3): δ = 1.07-1.61 (m, 18H, (CH2)9); 2.02 (m, 2H, CH2CF2); 3.17 (t, 3J(H,H) = 6.3 Hz, 2H, OCH2); 3.74-4.13 (m, 10H, OCH2, OCH); 6.95 (d, 3J(H,H) = 8.5 Hz, 4H, ArH); 7.17 (t, 3J(H,H) = 7.6 Hz, 1H, ArH); 7.26 (d, 3J(H,H) = 7.5 Hz, 2H, ArH); 7.54 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH); 13C-NMR (100 MHz, CDCl3): δ = 20.29, 25.94, 29.27, 29.33, 29.41, 29.50, 29.61, 29.62, 29.98, 31.06 (CH2); 63.85, 63.85, 69.33, 69.33 (OCH2); 70.69, 70.69 (OCH); 72.98 (OCH2); 114.13, 114.13, 114.13, 114.13, 124.03, 129.70, 129.70, 130.67, 130.67, 130.67, 130.67, 132.05, 132.05, 135.47, 135.47, 154.05, 157.58, 157.58 ppm; 19F-NMR (200 MHz, CDCl3): δ = -81.17 (t, 3J(H,H) = 9.9 Hz, 3F, CF3); -114.72 (m, 2F, CF2CH2); -122.21 (s, 6F, CF2); -123.10 (s, 2F, CF2); -123.90 (s, 2F, CF2); -126.47 ppm (s, 2F, CF2); elemental analysis: C43H47F17O7 (0.5 H2O) requires: C 51.24, H 4.80, N 0.00 %; found: C 51.28, H 4.95, N 0.00 %. 4.4 Compounds 2 1,3-Bis[4-(2,3-dihydroxypropyloxy)phenylethynyl]-2-dodecyloxybenzene (2a): A mixture of 0.3 g (0.41 mmol) 1,3-bis{4-[(2,2-dimethyl-1,3-dioxolane-4-yl)methoxy]-phenylethynyl}-2-dodecyloxybenzene, 40 ml methanol and 50 mg (0.2 mmol) pyridinium 4-toluensulphonate is stirred for five hours under reflux. The reaction mixture is then evaporated under reduced pressure to a small volume and the residue is taken up in water and diethyl ether. The organic layer is separated and the water phase is extracted two times with diethyl ether. The combined organic phases are washed with brine, dried over sodium sulphate and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: THF) and crystallized from CH2Cl2. Yield: 168 mg (0.26 mmol; 63 %); white solid; 1H-NMR (400 MHz, CDCl3): δ = 0.86 (t, 3J(H,H) = 6.8 Hz, 3H, CH3); 1.20-1.29 (m, 16H, (CH2)8); 1.53 (quin, 3J(H,H) = 8.0 Hz, 2H, OCH2CH2CH2); 1.86 (quin, 3J(H,H) = 7.6 Hz, 2H, OCH2CH2); 3.73-3.87 (m, 4H, OCH2); 4.05-4.12 (m, 6H, OCH2, OCH); 4.28 (t, 3J(H,H) = 6.4 Hz, 2H, OCH2CH2); 6.88 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.00 (t, 3J(H,H) = 7.7 Hz, 1H, ArH); 7.41 (d, 3J(H,H) = 7.7 Hz, 2H, ArH); 7.45 ppm (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 13C-NMR (100 MHz, CDCl3): δ = 14.19 (CH3); 22.77, 26.43, 29.43, 29.70, 29.73, 29.73, 29.73, 29.78, 30.69, 32.00 (CH2); 63.62, 63.62, 69.30, 69.30 (OCH2); 70.36, 70.36 (OCH); 74.46 (OCH2); 84.61, 84.61, 93.40, 93.40 (C≡C); 114.58, 114.58, 114.58, 114.58, 116.26, 116.26, 117.98, 117.98, 123.17, 132.96, 132.96, 132.96, 132.96, 132.96, 132.96, 158.39, 158.39, 160.84 ppm; elemental analysis: C40H50O7 (0.5 H2O) requires: C 73.70, H 7.89, N 0.00 %; found: C 73.56, H 7.91, N 0.00 %.

S12

1,3-Bis[4-(2,3-dihydroxypropyloxy)phenylethynyl]-2-(5,5,6,6,7,7,8,8,9,9,10,10,10-trideca-fluorodecyloxy)benzene (2b): Purified by column chromatography on silica gel (eluent: EtOAc) and crystallized from CH2Cl2/THF. Yield: 0.11 g (0.13 mmol; 34 %); colorless solid; 1H-NMR (400 MHz, CDCl3): δ = 1.93-1.94 (m, 4H, (CH2)2CH2CF2); 2.11 (m, 2H, CH2CF2); 3.72-3.86 (m, 4H, OCH2); 4.04-4.31 (m, 8H, OCH2, OCH); 6.88 (d, 3J(H,H) = 8.7 Hz, 4H, ArH); 7.03 (t, 3J(H,H) = 7.7 Hz, 1H, ArH); 7.41-7.45 ppm (m, 6H, ArH); 19F-NMR (200 MHz, CDCl3): δ = -81.18 (t, 3J(H,H) = 9.9 Hz, 3F, CF3); -114.72 (m, 2F, CF2CH2); -122.30 (s, 2F, CF2); -123.26 (s, 2F, CF2); -123.90 (s, 2F, CF2); -126.50 ppm (s, 2F, CF2); 13C-NMR (100 MHz, CDCl3): δ = 17.72, 30.24, 30.96 (CH2); 63.65, 63.65, 69.35, 69.35 (OCH2); 70.38, 70.38 (OCH); 73.41 (OCH2); 84.34, 84.34, 93.61, 93.61 (C≡C); 114.68, 114.68, 114.68, 114.68, 116.05, 116.05, 118.02, 118.02, 123.55, 132.97, 132.97, 132.97, 132.97, 133.14, 133.14, 158.56, 158.56, 160.42 ppm; elemental analysis: C38H33F13O7 requires: C 53.78, H 3.92, N 0.00 %; found: C 53.67, H 3.72, N 0.00 %. 1,3-Bis[4-(2,3-dihydroxypropyloxy)phenylethynyl]-2-(12,12,13,13,14,14,15,15,16,16,17,-17,18,18,19,19,19-heptadecafluorononadecyloxy)benzene (2c): Purified by column chromatography on silica gel (eluent: EtOAc) and crystallized from CH2Cl2. Yield: 69 mg (0.066 mmol; 57 %); colorless solid; 1H-NMR (400 MHz, CDCl3): δ = 1.22-1.32 (m, 12H, (CH2)6); 1.52-1.56 (m, 4H, OCH2CH2CH2, CH2CH2CF2); 1.86 (quin, 3J(H,H) = 7.1 Hz, 2H, OCH2CH2); 2.02 (m, 2H, CH2CF2); 3.72-3.86 (m, 4H, OCH2); 4.05-4.12 (m, 6H, OCH2, OCH); 4.29 (t, 3J(H,H) = 6.3 Hz, 2H, OCH2CH2); 6.88 (d, 3J(H,H) = 8.9 Hz, 4H, ArH); 7.00 (t, 3J(H,H) = 7.8 Hz, 1H, ArH); 7.41 (d, 3J(H,H) = 7.9 Hz, 2H, ArH); 7.45 ppm (d, 3J(H,H) = 8.7 Hz, 4H, ArH); 19F-NMR (200 MHz, CDCl3): δ = -81.17 (t, 3J(H,H) = 9.9 Hz, 3F, CF3); -114.72 (m, 2F, CF2CH2); -122.21 (s, 6F, CF2); -123.08 (s, 2F, CF2); -123.88 (s, 2F, CF2); -126.45 ppm (s, 2F, CF2); 13C-NMR (100 MHz, CDCl3): δ = 20.25, 26.41, 29.22, 29.34, 29.47, 29.59, 29.65, 29.65, 30.67, 31.02 (CH2); 63.61, 63.61, 69.31, 69.31 (OCH2); 70.34, 70.34 (OCH); 74.42 (OCH2); 84.62, 84.62, 93.39, 93.39 (C≡C); 114.58, 114.58, 114.58, 114.58, 116.27, 116.27, 117.97, 117.97, 123.18, 132.96, 132.96, 132.96, 132.96, 133.00, 133.00, 158.41, 158.41, 160.82 ppm; elemental analysis: C47H47F17O7 requires: C 53.92, H 4.53, N 0.00 %; found: C 53.65, H 4.34, N 0.00 %. 5. References [S1] A.Immirzi, B. Perini, Acta Cryst. Sect. A 1977, 33, 216. [S2] A. I. Kitaigorodski, “Molekülkristalle”, Akademieverlag Berlin, 1979. [S3] F. G. Pope, A. S. Wood, J. Chem. Soc., Trans. 1912, 101, 1823. [S4] G. Johansson, V. Percec, G. Ungar, J. P. Zhou, Macromolecules 1996, 29, 646. [S5] M. Kölbel, T. Beyersdorff, C. Tschierske, S. Diele, J. Kain, Chem. Eur. J. 2000, 6, 3821. [S6] M. Kölbel, T. Beyersdorff, X.-H. Cheng, C. Tschierske, J. Kain, S. Diele, J. Am. Chem.

Soc 2001, 123, 680.