Supplementary Information

Transcription

1 Supplementary Information Arrays of giant octagonal and square cylinders by liquid crystalline self-assembly of X-shaped polyphilic molecules Feng Liu 1,, Robert Kieffer 2, Xiangbing Zeng 1, Karsten Pelz 2, Marko Prehm 2, Goran Ungar 1,3, * and Carsten Tschierske 2, * 1 Department of Materials Science and Engineering, University of Sheffield, Mappin Street, Sheffield S1 3JD, Great Britain. g.ungar@sheffield.ac.uk 2 Institute of Chemistry, Martin-Luther-University Halle-Wittenberg, Kurt-Mothes Str. 2, D Halle, Germany. carsten.tschierske@chemie.uni-halle.de 3 WCU program Chemical Convergence for Energy & Environment, School of Chemical and Biological Engineering, Seoul National University, Seoul, Korea. Current address: State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an , China.

2 (a) (b) p4gm M Iso Cr p4gm Iso (c) (d) Cr p4gm Iso p4gm M Iso Supplementary Figure S1 DSC traces of compound 1a. (a) Complete heating scan with 10 K min -1. (b) p4gm-to-iso transition region with 1 K min -1. (c) Complete cooling cooling with 10 K min -1. (d) Iso-to-p4gm transition region with 1 K min -1.

3 (a) Cr p4gm Iso M (b) M Cr p4gm Iso Supplementary Figure S2 DSC traces of compound 1b. (a) Complete heating scan with 10 K min -1. (b) Complete cooling cooling with 10 K min -1.

4 (a) Cr p4gm Iso (b) Cr p4gm Iso Supplementary Figure S3 DSC traces of compound 1c. (a) Complete heating scan with 10 K min -1. (b) Complete cooling cooling with 10 K min -1.

5 (a) Cr p4gm Iso (b) Cr p4gm Iso Supplementary Figure S4 DSC traces of compound 1d. (a) Complete heating scan with 10 K min -1. (b) Complete cooling cooling with 10 K min -1.

6 (a) p6mm Iso (b) p6mm Iso Supplementary Figure S5 DSC traces of compound 2a. (a) Complete heating scan with 10 K min -1. (b) Complete cooling cooling with 10 K min -1.

7 (a) (b) (c) (d) Supplementary Figure S6 X-ray diffraction patterns of partially aligned samples of the Col squ /p4gm phase of compounds 1a and 1b at 110 C. (a) 2D pattern of 1a. (b) θ-scan of the diffraction pattern of 1a with the d value for the maximum of the diffuse outer scattering. (c) 2D pattern of 1b. (d) θ-scan of the diffraction pattern of 1b with the d value for the maximum of the diffuse outer scattering.

8 (a) (b) (c) Supplementary Figure S7 SAXS diffractograms of the Col squ /p4gm phase (synchrotron source). (a) Compound 1b at T = 95 o C. (b) Compound 1c at T = 90 o C. (c) Compound 1d at T = 100 o C.

9 Supplementary Figure S8 Grazing incidence small-angle X-ray scattering (GISAXS) pattern. The Col squ /p4gm phase of compound 1d recored at T = 100 o C (synchrotron source). The wide white horizontal and vertical lines are gaps between the detector elements. The reciprocal lattice is superimposed. In the area of the LC film irradiated in this pattern the lattice plane in contact with the substrate is (110).

10 (a) (b) (c) Supplementary Figure S9 Data of Compound 2a. (a) SAXS diffractogram of the Col hex /p6mm phase at 100 o C (synchrotron source, a hex = 4.0 nm). (b) Texture between crossed polarizers at the same temperature - the dark areas are homeotropically aligned regions indicating optical uniaxiality of the mesophase. (c) Same texture with -retarder plate, the indicatrix orientation in the compensator is the same as in Fig. 2b.

11 L Supplementary Figure S10 Molecular length. CPK molecular models showing compound 1d with L = 2.1 nm.

12 (a) (b) 1a: (0π0) 1a: (00π) (c) (d) 1a: (π0π) 1a: (ππ0) (e) (f) 1a: (00ππ0-π0ππ) 1d: (00ππ0ππ-ππ) Supplementary Figure S11 Calculated electron density maps using different structure factor phase combinations. (a-d) The four coarse-grain maps of the p4gm honeycomb of compound 1a based on the three strongest reflections (11), (20) and (21) using the phase combinations listed; (e) and (f) Fine-grain maps of compounds 1a and 1d, respectively, using all reflections up to (43) with phase angles given below the maps in order of appearance in Supplementary Tables S1 and S4; these phase angles are the exact reverse of those used in the accepted maps in Figures 3b,c. Phases of unobserved reflections appear as - in the listed phase sequences. Electron density color code: purple/blue = high, red/yellow = low, green = medium.

13 Supplementary Table S1 Compound 1a. Experimental and calculated d-spacings, relative integrated intensities, and phases used in the reconstruction of electron densities for the Col squ /p4gm phase at 100ºC. All intensities values are Lorentz and multiplicity corrected. (hk) d obs. spacing (nm) d cal. spacing (nm) intensity phase a (11) π (20) π (21) (22) (31) π (32) - b (40) (41) π (42) (43) (51) (52) (53) / (60) / (62) (54) (63) / (55) (64) / (73) (65) (80) / (82) / (66) / a squ = 9.37 nm a Phase angle of the structure factor used in electron density reconstruction. b Not observed experimentally.

14 Supplementary Table S2 Compound 1b. Experimental and calculated d-spacings, relative integrated intensities, and phases used in the reconstruction of electron densities for the Col squ /p4gm phase at 95ºC. All intensities values are Lorentz and multiplicity corrected. (hk) d obs. spacing (nm) d cal. spacing (nm) intensity phase (11) π (20) π (21) (22) (31) π (32) (40) (41) (42) (43) (51) (52) (53) / (60) / (62) (54) / (63) / (55) (64) / (73) / (65) / (80) (82) (66) a squ = 9.67 nm

15 Supplementary Table S3 Compound 1c. Experimental and calculated d-spacings, relative integrated intensities, and phases used in the reconstruction of electron densities for the Col squ /p4gm phase at 90ºC. All intensities values are Lorentz and multiplicity corrected. (hk) d obs. spacing (nm) d cal. spacing (nm) intensity phase (11) π (20) π (21) (22) (31) π (32) (40) (41) (42) (43) (51) (52) (53) / (60) / (62) / (54) (63) / (55) / (64) / (73) (65) (80) (82) (66) a squ = 9.79 nm

16 Supplementary Table S4 Compound 1d. Experimental and calculated d-spacings, relative integrated intensities, and phases used in the reconstruction of electron densities for the Col squ /p4gm phase at 100ºC. All intensities values are Lorentz and multiplicity corrected. (hk) d obs. spacing (nm) d cal. spacing (nm) intensity phase (11) π (20) π (21) (22) (31) π (32) (40) (41) (42) (43) (51) (52) (53) / (60) / (62) / (54) (63) / (55) / (64) / (73) (65) (80) (82) (66) a squ = 9.83 nm

17 Supplementary Table S5 Compound 2a. Experimental and calculated d-spacings, relative integrated intensities, and phases used in the reconstruction of electron densities for the Col hex /p6mm phase at 100 ºC. All intensity values are Lorentz and multiplicity corrected. (hk) d obs. spacing (nm) d cal. spacing (nm) intensity phase (10) (11) (20) (21) π (30) π a hex = 4.00 nm Supplementary Table S6 Unit cell area and area per molecule (wall) for compounds 2a-d forming hexagonal honeycombs (p6mm) with hexagon sides just one molecule long Compound/phase n Lattice Parameter (nm) Unit cell area (nm 2 ) Number of molecules j a Area/molecule A (nm 2 ) 2a/p6mm b/p6mm c/p6mm d/p6mm a assumed

18 Supplementary Table S7 Comparison of molecular volumes and areas for compounds 1a-d and 2a-d. Volumes are obtained from molecular models using the crystal volume increments 38, a Compound V mol [nm 3 ] Compound V mol [nm 3 ] 2a Volume difference (%) Area difference (%) b 1a b b c c d d a The difference in molecular volumes is due to the four hydrogens being replaced by four fluorines. b Assuming A 1 /A 2 = (V 1 /V 2 ) 2/3 Supplementary Table S8. Unit cell area, area per molecule, and number of molecules per unit cell for the p4gm phase of compounds 1a-d. Number of Lattice Parameter Unit cell area Area/molecule Compound/phase (nm) (nm 2 ) A (nm 2 ) a molecules per unit cell j 1a/p4gm b/p4gm c/p4gm d/p4gm a Taken as the area per molecule of compound 2 closest in volume to that of the comound 1 in question, i.e. 2b for 1a, 2c for 1b, and 2d for 1c, and applying the correction in the last column of Table S7.

19 Supplementary Methods Choice of phase combination Using the three dominant reflections (11), (20) and (21) of compound 1a, Supplementary Table S1, for this centrosymmetric plane group (p4gm), we obtain 2 3 = 8 coarse-grain electron density maps. Pairs of phase combinations (000) - (00 ), (0 0) - (0 ), ( 00) - ( 0 ), and ( 0) - ( ), give the same maps except for a shift in the origin of the unit cell from (0, 0) to (1/2, 1/2). Therefore, the number of possible coarse-grain maps reduces to four (Supplementary Figure S11a-d). As can be seen, maps (00 ) and (0 0) are simply the inverse of maps ( 0) and ( 0 ), respectively. We note that the effect of the remaining reflections, i.e. those beyond the three strongest, on the electron density maps is only minor. The key features are contained in the coarse-grain maps. One of these features is the large area of the maxima and minima, which can only be fitted by models with giant polygons, i.e. honeycombs with walls more than one molecule long. In fact the possible layout of the walls is similar for all phase combinations; the difference is only in the possibility of the giant octagons being bridged (extra walls across their width) or unbridged. In Supplementary Figures S11a-d schematic molecules are superimposed on the maps, suggesting the potential structures. Below we discuss the merits of each of the four coarse-grain maps and associated structural models in turn. In the 0 0 and 0 maps we drew molecules bridging the octagon, dividing it into a central rectangle and two trapezoids. The reason is that the extremes in electron density contained within these rectangles, i.e. the high maximum (R F -chains, 0 ) or the deep minimum (R H chains, 0 0) could not have been due to merely two chains entering from the sides of the octagon. The chains creating the electron density extremes would have to be more numerous, hence coming from the bridging molecules. However, as these extra 8 bridging molecules would have increased the number of molecules from j = 20 to j = 28, an unmissable increase of 40%, these two structures must be dismissed, as the determined value of j is (see Supplementary Table S8). Besides, another reason for dismissing the 0 0 and 0 maps is the fact that they have only shallow maxima/minima at the positions of the giant squares, where pronounced ones would be expected, considering that eight equal chains feed into them. The 0 map is the coarse-grain version of the map in Figure 3b in the main text, i.e. the one chosen as the correct one in this work. The 00 is its inverse. The 00 map implies the same octagon/square structure as the accepted 0, except that the R F and R H chains swap places. It can be shown easily that the area per side-chain of an ideal giant square with straight walls of zero thickness is 0.5 L 2, whereas that in the octagon is 0.58 L 2. Since the R F chains are undoubtedly larger than the R H chains, they must be occupying the octagons rather than the squares, hence the 0 map remains the only viable option.

20 A further check is carried out after the remaining reflections were included. The resulting fine-grain versions of the 00 map for compounds 1a and 1d are compared in Supplementary Figures S11e,f, applying the exact reverse of the full set of phases used in the accepted maps in Figures 3b,c (phases are listed in Supplementary Tables S1 and S4). Since compound 1d has much longer alkyl chains (C 16 H 33 ) than 1a (C 10 H 21 ), one would expect the low-density (red) areas to be larger in Supplementary Figure S11f compared to those in Supplementary Figure S11e; instead it is the highdensity (blue-purple) areas that are larger in Supplementary Figure S11f. This discrepancy with expectation gives additional support to the 0 map, shown in Figures 3b, c, being the correct choice. Synthesis of the materials 4-Benzyloxy-2,5-dibromo-1-alkoxybenzenes 3a-d General procedure for the WILLIAMSON etherification: To a solution of 4-benzyloxy-2,5- dibromophenol 25,39 (1eq) in dry CH 3 CN the appropriate bromoalkane (1.1eq) was added under an argon atmosphere. After the addition of K 2 CO 3 (5eq) and a catalytic amount of Bu 4 NI the mixture was refluxed for 6 hours. After cooling to r.t. H 2 O (50-70 ml) was added and the mixture was stirred for 15 minutes. The precipitated product was filtered off and washed with a small amount of H 2 O. The crude product was purified by crystallisation from petrol ether. 4-Benzyloxy-2,5-dibromo-1-decyloxybenzene (3a) 25 : Synthesized and purified according to the general procedure from 4-benzyloxy-2,5-dibromophenol (3 g; 8.38 mmol), 1-bromodecane (2.04 g; 9.22 mmol), K 2 CO 3 (5.8 g; 42 mmol), Bu 4 NI (100 mg), CH 3 CN (50 ml). Yield: 3.39 g (81 %), colorless solid; mp.: 52 C 25 ; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 2H, Ar-H), (m, 2H, Ar-H), (m, 1H, Ar-H), 7.14 (s, 1H, Ar-H), 7.09 (s, 1H, Ar-H), 5.05 (s, 2H, OCH 2 Ph), 3.94 (t, 3 J = 6.43 Hz, 2H, OCH 2 ), (m, 2H, OCH 2 CH 2 ), (m, 2H, OCH 2 CH 2 CH 2 ), (m, 12H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 4-Benzyloxy-2,5-dibromo-1-dodecyloxybenzene (3b) 40 : Synthesized and purified according to the general procedure from 4-benzyloxy-2,5-dibromophenol (600 mg; 1.67 mmol), 1-bromododecane (460 mg; 1.84 mmol), K 2 CO 3 (231 mg; 8.34 mmol), Bu 4 NI (50 mg), CH 3 CN (50 ml). Yield: 750 mg (85 %), colorless solid; mp.: 55 C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 2H, Ar-H), (m, 2H, Ar-H), (m, 1H, Ar-H), 7.14 (s, 1H, Ar-H), 7.09 (s, 1H, Ar-H), 5.05 (s, 2H, OCH 2 Ph), 3.93 (t, 3 J = 6.43 Hz, 2H, OCH 2 ), (m, 2H, OCH 2 CH 2 ), (m, 2H, OCH 2 CH 2 CH 2 ), (m, 16H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ).

21 4-Benzyloxy-2,5-dibromo-1-tetradecyloxybenzene (3c): Synthesized and purified according to the general procedure from 4-benzyloxy-2,5-dibromophenol (2 g; 5.60 mmol), 1-bromotetradecane (1.70 g; 6.1 mmol), K 2 CO 3 (3.86 g; 28 mmol), Bu 4 NI (100 mg), CH 3 CN (50 ml). Yield: 2.70 g (87 %), colorless solid; mp.: 58.5 C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 2H, Ar-H), (m, 2H, Ar-H), (m, 1H, Ar-H), 7.14 (s, 1H, Ar-H), 7.09 (s, 1H, Ar-H), 5.05 (s, 2H, OCH 2 Ph), 3.94 (t, 3 J = 6.43 Hz, 2H, OCH 2 ), (m, 2H, OCH 2 CH 2 ), (m, 2H, OCH 2 CH 2 CH 2 ), (m, 20H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 4-Benzyloxy-2,5-dibromo-1-hexadecyloxybenzene (3d) 39 : Synthesized and purified according to the general procedure from 4-benzyloxy-2,5-dibromophenol (1.1 g; 3.07 mmol), 1- bromohexadecane (1.03 g; 3.37 mmol), K 2 CO 3 (2.12 g; 15.4 mmol), Bu 4 NI (100 mg), CH 3 CN (50 ml). Yield: 1.47 g (82 %), colorless solid; mp.: 64 C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 2H, Ar-H), (m, 2H, Ar-H), (m, 1H, Ar-H), 7.14 (s, 1H, Ar-H), 7.09 (s, 1H, Ar-H), 5.05 (s, 2H, OCH 2 Ph), 3.94 (t, 3 J = 6.54 Hz, 2H, OCH 2 ), (m, 2H, OCH 2 CH 2 ), (m, 2H, OCH 2 CH 2 CH 2 ), (m, 24H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 5 -Benzyloxy-4,4 -bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -alkoxy-p-terphenyls 4a-d General procedure for the SUZUKI cross coupling reaction: Under an argon atmosphere the appropriate 4-benzyloxy-2,5-dibromo-1-alkoxybenzene 3a-d (1eq) and the 4-(2,2-dimethyl-1,3- dioxolane-4-ylmethoxy)benzeneboronic acid 41 ; 2.2 eq) were dissolved in ethyleneglycoldimethylether. The same volume of sat. aqu. NaHCO 3 solution was added under an argon atmosphere. After addition of the catalyst Pd(PPh 3 ) 4 (3mol%, with respect to the dibromo compound 3a-d) the reaction mixture was refluxed for 10 h. After cooling to room temperature, the solvent was evaporated and the residue was dissolved in chloroform. The resulting solution was washed with H 2 O and brine. After separation and drying over Na 2 SO 4 the solvent was evaporated. The crude product was purified by column chromatography with CHCl 3 as solvent and finally crystallised from petrol ether. 5 -Benzyloxy-4,4 -bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -decyloxy-p-terphenyl (4a): Synthesized and purified according to the general procedure from 3a (3 g; 6.02 mmol), 4-(2,2- dimethyl-1,3-dioxolane-4-ylmethoxy)benzeneboronic acid (3.34 g; mmol), Pd(PPh 3 ) 4 (210 mg; 0.18 mmol), ethyleneglycoldimethylether (100 ml), sat. aqu. NaHCO 3 solution (100 ml). Yield: 3.56 g (79 %), colorless solid; mp.: 79 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.55 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.48 (d, 3 J = 8.92 Hz, 2H, Ar-H), (m, 5H, Ar-H), 7.00 (s, 1H, Ar-H), (m, 5H, Ar-H), 4.97 (s, 2H, O-CH 2 Ph), (m, 2H, CHO), (m, 2H, CH 2 O),

22 (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 4H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.48 (s, 6H, CH 3 ), 1.41 (s, 6H, CH 3 ), (m, 14H, CH 2 ), 0.88 ppm (t, 3 J = 6.95 Hz, 3H, CH 3 ). 5 -Benzyloxy-4,4 -bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -dodecyloxy-p-terphenyl (4b): Synthesized and purified according to the general procedure from 3b (600 mg; 1.14 mmol), 4- (2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)benzeneboronic acid (632 mg; 2.5 mmol), Pd(PPh 3 ) 4 (40 mg; mmol), ethyleneglycoldimethylether (40 ml), sat. aqu. NaHCO 3 solution (40 ml). Yield: 720 mg (81 %), colorless solid; mp.: 82 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.54 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.47 (d, 3 J = 8.72 Hz, 2H, Ar-H), (m, 5H, Ar-H), 6.99 (s, 1H, Ar-H), (m, 5H, Ar-H), 4.96 (s, 2H, O-CH 2 Ph), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 4H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.47 (s, 6H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 18H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 5 -Benzyloxy-4,4 -bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -tetradecyloxy-p-terphenyl (4c): Synthesized and purified according to the general procedure from 3c (2.6 g; 4.69 mmol), 4- (2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)benzeneboronic acid (2.6 g; 10.3 mmol), Pd(PPh 3 ) 4 (163 mg; 0.14 mmol), ethyleneglycoldimethylether (80 ml), sat. aqu. NaHCO 3 solution (80 ml). Yield: 2.75 g (73 %), colorless solid; mp.: 83 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.54 (d, 3 J = 8.92 Hz, 2H, Ar-H), 7.47 (d, 3 J = 8.92 Hz, 2H, Ar-H), (m, 5H, Ar-H), 6.99 (s, 1H, Ar-H), (m, 5H, Ar-H), 4.96 (s, 2H, O-CH 2 Ph), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 4H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.47 (s, 6H, CH 3 ), 1.41 (s, 6H, CH 3 ), (m, 22H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 5 -Benzyloxy-4,4 -bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -hexadecyloxy-p-terphenyl (4d): Synthesized and purified according to the general procedure from 3d (1.45 g; 2.49 mmol), 4- (2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)benzeneboronic acid (1.38 g; 5.48 mmol), Pd(PPh 3 ) 4 (89 mg; mmol), ethyleneglycoldimethylether (50 ml), sat. aqu. NaHCO 3 solution (50 ml). Yield: 1.63 g (78 %), colorless solid; mp.: 85 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.54 (d, 3 J = 8.92 Hz, 2H, Ar-H), 7.48 (d, 3 J = 8.92 Hz, 2H, Ar-H), (m, 5H, Ar-H), 6.99 (s, 1H, Ar-H), (m, 5H, Ar-H), 4.96 (s, 2H, O-CH 2 Ph), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 4H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.47 (s, 6H, CH 3 ), 1.41 (s, 6H, CH 3 ), (m, 26H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ).

23 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -alkoxy-p-terphenyl-2 -ols 5a-d General procedure for cleavage of the benzyl protective group: Under an argon atmosphere the appropriate benzyl protected phenol 4a-d was dissolved in ethyl acetate and Pd/C (10 % Pd) was added. After rinsing with hydrogen (3x) the hydrogen pressure was set to 3.2 bar and the temperature was set to 45 C. After 8 h the solution was filtered and the filtrate was washed with hot ethyl acetate. The solvent was evaporated and the crude product was purified by crystallisation from ethyl acetate/petrol ether = 5:1, v/v. 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -decyloxy-p-terphenyl-2 -ol (5a): Synthesized and purified according to the general procedure from 4a (3.5 g; 4.65 mmol), Pd/C (200 mg), ethyl acetate (100 ml). Yield: 2.43 g (79 %), colorless solid; mp.: 88 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.51 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.42 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.02 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.93 (s, 1H, Ar-H, overlapped), 6.93 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.81 (s, 1H, Ar- H), 4.87 (s, 1H, OH), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), 3.87 (t, 3 J = 6.43 Hz, 2H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.47 (s, 6H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 14H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -dodecyloxy-p-terphenyl-2 -ol (5b): Synthesized and purified according to the general procedure from 4b (2.3 g; 2.94 mmol), Pd/C (200 mg), ethyl acetate (100 ml). Yield: 1.74 g (86 %), colorless solid; mp.: 87 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.51 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.42 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.02 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.92 (s, 1H, Ar-H, overlapped), 6.93 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.80 (s, 1H, Ar- H), 4.82 (s, 1H, OH), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), 3.84 (t, 3 J = 6.54 Hz, 2H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.46 (s, 6H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 18H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -tetradecyloxy-p-terphenyl-2 -ol (5c): Synthesized and purified according to the general procedure from 4c (2.7 g; 3.34 mmol), Pd/C (200 mg), ethyl acetate (100 ml). Yield: 2.20 g (92 %), colorless solid; mp.: 83 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.51 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.42 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.02 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.93 (s, 1H, Ar-H, overlapped), 6.93 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.81 (s, 1H, Ar- H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m,

24 2H, CH 2 O), (m, 2H, CH 2 O), 3.84 (t, 3 J = 6.43 Hz, 2H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.47 (s, 6H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 22H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). Semiperfluorinated alkyl bromides 7/10 and 7/12 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -hexadecyloxy-p-terphenyl-2 -ol (5d): Synthesized and purified according to the general procedure from 4d (820 mg; 0.98 mmol), Pd/C (100 mg), ethyl acetate (50 ml). Yield: 635 mg (87 %), colorless solid; mp.: 78 C; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.51 (d, 3 J = 8.92 Hz, 2H, Ar-H), 7.42 (d, 3 J = 8.72 Hz, 2H, Ar-H), 7.02 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.93 (s, 1H, Ar-H, overlapped), 6.93 (d, 3 J = 8.72 Hz, 2H, Ar-H), 6.81 (s, 1H, Ar-H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 2H, CH 2 O), 3.84 (t, 3 J = 6.54 Hz, 2H, CH 2 O), (m, 2H, OCH 2 CH 2 ), 1.47 (s, 6H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 26H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ). 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-Pentacosafluorooctadecan-1-ol (6/12): The Pd catalyzed addition of perfluoroalkyliodides to the double bonds, followed by reduction, as reported by JOHANSSON et al. 42 was used for the synthesis of the semiperfluorinated alcohol. Accordingly, under an argon atmosphere hex-5-en-1-ol (0.67 g; 6.7 mmol) was dissolved in dry hexane (100 ml) and the solution was degassed in an ultra sonic bath under an argon atmosphere for 30 min. After the addition of 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-pentacosafluoro-12-iodododecane (5.0 g; 6.7 mmol) the mixture was degassed further for 5 min. Then the mixture was cooled to T = -100 C and the flask was evaporated, refilled with argon and warmed up to room temperature. This procedure was repeated three times. Then the solution was allowed to come to T = 0 C and the catalyst Pd(PPh 3 ) 4 (0.39 g; 0.34 mmol) was added under an argon atmosphere. The mixture was stirred at r.t. for 100 hours. After this the mixture was filtered through silica gel and the residue was washed with Et 2 O (150 ml). The solvent was removed und reduced pressure and the residue was taken up in Et 2 O (50 ml). This solution was added dropwise to a suspension of LiAlH 4 (0.20 g; 5.3 mmol) in dry Et 2 O (50 ml) at such a rate to maintain the solution at reflux. The mixture was heated to reflux for additionally 6 h, cooled to room temperature and the unreacted LiAlH 4 was hydrolyzed by careful addition of water. Then 30 % aqueous H 2 SO 4 (20 ml) was added to dissolve all precipitated solids. The organic layer was separated and the aqueous layer was extracted with Et 2 O (3x50 ml), the combined organic layers were washed with 10 % aqueous Na 2 S 2 O 3 until the aqueous layer remained colorless. After washing with water (2x100 ml) and brine (100 ml), the solution was dried

25 over anhydrous Na 2 SO 4, the solvent was removed and the crude product was purified by column chromatography (silica gel, eluent: CHCl 3 /MeOH = 10/0.2 (v/v). Yield: 2.5 g (52 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = 3.64 (t, 3 J = 6.54 Hz, 2H, CH 2 OH), (m, 2H, CH 2 CF 2 ), (m, 4H, CH 2 CH 2 OH, CH 2 CH 2 CF 2 ), ppm (m, 4H, CH 2 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.88 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ). 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-Henicosafluorohexadecan-1-ol (6/10) 43, 44 : Synthesized and purified in an analogues way as 6/12 from 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-henicosafluoro-10-iododecane (5.0 g; 7.74 mmol), hex-5- en-1-ol (0.77 g; 7.7 mmol), Pd(PPh 3 ) 4 (0.45 g; 0.39 mmol), hexane (100 ml), LiAlH 4 (0.23 g; 6.1 mmol), diethylether (100 ml). Yield: 3.4 g (71 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = 3.64 (t, 3 J = 6.43 Hz, 2H, CH 2 OH), (m, 2H, CH 2 CF 2 ), (m, 4H, CH 2 CH 2 OH, CH 2 CH 2 CF 2 ), ppm (m, 4H, CH 2 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.13 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 10F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ). 18-Bromo-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-pentacosafluoroocta-decane (7/12): To a suspension of 6/12 (2.4 g; 3.33 mmol) in HBr (47 %; 100 ml) Bu 4 NHSO 4 (0.5 g) and conc. H 2 SO 4 (2 ml) was added. The mixture was stirred at T = 100 C for 24 hours and then cooled to room temperature. After addition of water (100 ml) and extraction with Et 2 O (3x 50 ml) the combined organic layers were washed with water (100 ml) and dried over anhydrous Na 2 SO 4. The solvent was removed under reduced pressure and the crude product was purified by column chromatography (silica gel, eluent: petroleum ether). Yield: 2.2 g (84 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = 3.40 (t, 3 J = 6.64 Hz, 2H, CH 2 OH), (m, 2H, CH 2 CF 2 ), (m, 2H, CH 2 CH 2 OH), (m, 2H, CH 2 CH 2 CF 2 ), ppm (m, 4H, CH 2 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.24 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ). 16-Bromo-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-henicosafluorohexadecane (7/10) Synthesized and purified in an analogues way as 7/12 from 6/10 (3.3 g; 5.3 mmol), HBr (47%; 100 ml), H 2 SO 4 (98%; 100 ml), Bu 4 NHSO 4 (0.5 g). Yield: 2.85 g (78 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = 3.40 (t, 3 J = 6.74 Hz, 2H, CH 2 OH), (m, 2H, CH 2 CF 2 ), (m, 2H, CH 2 CH 2 OH), (m, 2H, CH 2 CH 2 CF 2 ), ppm (m, 4H, CH 2 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.97 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 10F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ).

26 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -semiperfluoroalkoxy)-5 -alkyloxy-pterphenyls 8a-d and 9a General procedure for etherification of the semiperfluorinated alkyl bromides: Under an argon atmosphere the appropriate phenol 5a-d (1 eq) and the appropriate semiperfloroalkylbromide 7/10 or 7/12 (1.05 eq) were dissolved in dry DMF (50 ml). After the addition of K 2 CO 3 (10 eq) and a catalytic amount of Bu 4 NI the reaction mixture was stirred at T = 80 C for 6 hours. After cooling to room temperature H 2 O (150 ml) was added and the precipitated product was filtered of and washed several times with water. The solid was dissolved in CHCl 3, filtered and the solvent was removed in vacuo. The crude product was purified by preparative centrifugal thin layer chromatography with petrol ether/chcl 3 = 1/1-0/1 (V/V) as eluents. 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -decyloxy-2 -(7,7,8,8,9,9,10,10,- 11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-p-terphenyl (8a): Synthesized and purified according to the general procedure from 5a (200 mg; 0.3 mmol), 7/12 (248 mg; 0.32 mmol), K 2 CO 3 (420 mg; 3 mmol), Bu 4 NI (50 mg), DMF (50 ml). Yield: 341 mg (83 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 4H, Ar- H), 6.94 (d, 3 J = 8.51 Hz, 4H, Ar-H), 6.91 (s, 2H, Ar-H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 8H, CH 2 O), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), 1.47 (s, 3H, CH 3 ), 1.46 (s, 3H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 18H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.22 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ). 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -dodecyloxy-2 -(7,7,8,8,9,9,10,10,- 11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-p-terphenyl (8b): Synthesized and purified according to the general procedure from 5b (200 mg; 0.29 mmol), 7/12 (238 mg; 0.3 mmol), K 2 CO 3 (400 mg; 2.9 mmol), Bu 4 NI (50 mg), DMF (50 ml). Yield: 315 mg (78 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 4H, Ar-H), 6.94 (d, 3 J = 8.72 Hz, 4H, Ar-H), 6.91 (s, 2H, Ar-H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 8H, CH 2 O), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), 1.47 (s, 3H, CH 3 ), 1.46 (s, 3H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 22H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 19 F- NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.88 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ).

27 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-2 -(7,7,8,8,9,9,10,10,11,11,12,12,- 13,13,14,14,15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-5 -tetradecyloxy-pterphenyl (8c): Synthesized and purified according to the general procedure from 5c (200 mg; 0.28 mmol), 7/12 (229 mg; 0.29 mmol), K 2 CO 3 (385 mg; 2.8 mmol), Bu 4 NI (50 mg), DMF (50 ml). Yield: 314 mg (79 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 4H, Ar-H), 6.94 (d, 3 J = 8.72 Hz, 4H, Ar-H), 6.91 (s, 2H, Ar-H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 8H, CH 2 O), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), 1.47 (s, 3H, CH 3 ), 1.46 (s, 3H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 26H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 19 F- NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.22 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ). 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -hexadecyloxy-2 -(7,7,8,8,9,9,10,10,- 11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-p-terphenyl (8d): Synthesized and purified according to the general procedure from 5d (200 mg; 0.27 mmol), 7/12 (220 mg; 0.28 mmol), K 2 CO 3 (370 mg; 2.7 mmol), Bu 4 NI (50 mg), DMF (50 ml). Yield: 285 mg (74 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 4H, Ar-H), 6.94 (d, 3 J = 8.51 Hz, 4H, Ar-H), 6.91 (s, 2H, Ar-H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 8H, CH 2 O), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), 1.47 (s, 3H, CH 3 ), 1.46 (s, 3H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 30H, CH 2 ), 0.86 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.91 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ). 4,4 -Bis(2,2-dimethyl-1,3-dioxolane-4-ylmethoxy)-5 -decyloxy-2 -(7,7,8,8,9,9,10,10,- 11,11,12,12,13,13,14,14,15,15,16,16,16-henicosafluorohexadecyloxy)-p-terphenyl 9a Synthesized and purified according to the procedure general procedure from 5a (250 mg; 0.38 mmol), 7/10 (271 mg; 0.4 mmol), K 2 CO 3 (520 mg; 3.8 mmol), Bu 4 NI (50 mg), DMF (50 ml). Yield: 369 mg (77 %), colorless solid; mp.: C; 1 H-NMR (CDCl 3, 400 MHz): δ = (m, 4H, Ar-H), 6.94 (d, 3 J = 8.30 Hz, 4H, Ar-H), 6.91 (s, 2H, Ar-H), (m, 2H, CHO), (m, 2H, CH 2 O), (m, 2H, CH 2 O), (m, 8H, CH 2 O), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), 1.47 (s, 3H, CH 3 ), 1.46 (s, 3H, CH 3 ), 1.40 (s, 6H, CH 3 ), (m, 18H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 19 F- NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.91 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 10F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ), ppm (s, 2F, CF 2 CF 3 ).

28 Compounds 1a-d and 2a General procedure for cleavage of the isopropylidene protective groups: To a solution of the appropriate bisacetonide (8a-d or 9a) in MeOH (50 ml) 10% HCl (10 ml) was added and the mixture was refluxed for 6 h. After cooling to room temperature sat. aqu. NaHCO 3 was added and the solvent removed in vacuo. The resulting suspension was filtered and the product was washed several times with water (30 ml each) and dried. The crude product was purified by preparative centrifugal thin layer chromatography (eluents: CHCl 3 /MeOH = 10/0.3, v/v) or crystallisation from MeOH. 3-[4 -(2,3-Dihydroxypropoxy)-5 -decyloxy-2 -(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,- 15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-p-terphenyl-4-yloxy]-propane-1,2- diol (1a): Synthesized according to the general procedure from 8a (330 mg; 0.24 mmol); purified by crystallisation from MeOH. Yield: 290 mg (93 %), colorless solid; 1 H-NMR (acetone-d 6, 400 MHz): δ = 7.55 (d, 3 J = 8.72 Hz, 4H, Ar-H), 7.00 (s, 2H, Ar-H), 6.98 (d, 3 J = 8.82 Hz, 4H, Ar-H), (m, 2H, CHO), (m, 10H, CH 2 OH, CH 2 O), (m, 6H, CH 2 O, OH), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), (m, 6H, CH 2 ), (m, 12H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 13 C-NMR (acetoned 6, 125 MHz): δ = , (C-4,21), , (C-11,14), , (C-9,16), (C-7,8,17,18), , (C-10,15), , (C-5,6,19,20), (C-12,13), 71.33, (C-2,23), 70.29, (C-3,22), 69.86, (CH 2 O), 64.09, (C-1,24), 32.53, 31.10, 30.23, 30.16, 30.09, 29.95, 29.91, 29.55, 29.40, 29.24, 29.20, 26.75, 26.42, 23.21, (CH 2 ), ppm (CH 3 ); 19 F-NMR (acetone-d 6, 188 MHz): δ = (t, 3 J = 9.91 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ) ppm (s, 2F, CF 2 CF 3 ); calculated for C 52 H 57 F 25 O 8 : C 48.61, H 4.47; found: C 48.26, H 4.68 %. 3-[4 -(2,3-Dihydroxypropoxy)-5 -dodecyloxy-2 -(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,- 14,15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-p-terphenyl-4-yloxy]-propane- 1,2-diol (1b): Synthesized according to the general procedure from 8b (310 mg; 0.22 mmol); purified by crystallisation from MeOH. Yield: 253 mg (87 %), colorless solid; 1 H-NMR (acetoned 6, 400 MHz): δ = 7.54 (d, 3 J = 8.82 Hz, 4H, Ar-H), 7.00 (s, 2H, Ar-H), 6.97 (d, 3 J = 8.72 Hz, 4H, Ar-H), (m, 2H, CHO), (m, 10H, CH 2 OH, CH 2 O), (m, 6H, CH 2 O, OH), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), (m, 6H, CH 2 ), (m, 16H, CH 2 ), 0.87 ppm (t, 3 J = 6.74 Hz, 3H, CH 3 ); 13 C-NMR (acetone-d 6, 100 MHz): δ = (C-4,21), , (C-11,14), (C-9,16), (C-

29 7,8,17,18), (C-10,15), , (C-5,6,19,20), (C-12,13), 71.42, (C- 2,23), (C-3,22), 70.08, (CH 2 O), 64.20, (C-1,24), 32.64, 31.55, 31.32, 31.11, 30.33, 30.32, 30.24, 30.08, 29.35, 26.88, 26.55, 23.34, (CH 2 ), ppm (CH 3 ); 19 F-NMR (acetone-d 6, 188 MHz): δ = (t, 3 J = 9.88 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ) ppm (s, 2F, CF 2 CF 3 ); calculated for C 54 H 61 F 25 O 8 : C 49.40, H 4.68; found: C 48.98, H 5.01 %. 3-[4 -(2,3-Dihydroxypropoxy)-2 -(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,- 17,17,18,18,18-pentacosafluorooctadecyloxy)-5 -tetradecyloxy-p-terphenyl-4-yloxy]propane- 1,2-diol (1c): Synthesized according to the general procedure from 8c (310 mg; 0.21 mmol); purified by crystallisation from MeOH. Yield: 262 mg (90 %), colorless solid; 1 H-NMR (acetoned 6, 400 MHz): δ = 7.55 (d, 3 J = 8.72 Hz, 4H, Ar-H), 7.00 (s, 2H, Ar-H), 6.98 (d, 3 J = 8.92 Hz, 4H, Ar-H), (m, 2H, CHO), (m, 10H, CH 2 OH, CH 2 O), (m, 6H, CH 2 O, OH), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), (m, 6H, CH 2 ), (m, 20H, CH 2 ), 0.87 ppm (t, 3 J = 6.85 Hz, 3H, CH 3 ); 13 C-NMR (acetone-d 6, 125 MHz): δ = , (C-4,21), , (C-11,14), (C-9,16), (C-7,8,17,18), , (C-10,15), , (C-5,6,19,20), (C-12,13), (C-2,23), 70.27, (C-3,22), 69.85, (CH 2 O), 64.08, (C-1,24), 32.51, 30.30, 30.25, 30.22, 30.20, 30.16, 30.01, 29.96, 29.90, 29.85, 29.54, 29.39, 29.24, 29.19, 26.73, 26.41, 23.20, (CH 2 ), ppm (CH 3 ); 19 F-NMR (acetone-d 6, 188 MHz): δ = (t, 3 J = 9.91 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ) ppm (s, 2F, CF 2 CF 3 ); calculated for C 56 H 65 F 25 O 8 : C 50.15, H 4.89; found: C 49.89, H 5.24 %. 3-[4 -(2,3-Dihydroxypropoxy)-5 -hexadecyloxy-2 -(7,7,8,8,9,9,10,10,11,11,12,12,13,13,- 14,14,15,15,16,16,17,17,18,18,18-pentacosafluorooctadecyloxy)-p-terphenyl-4-yloxy]-propane- 1,2-diol (1d): Synthesized according to the general procedure from 8d (280 mg; 0.19 mmol); purified by crystallisation from MeOH. Yield: 241 mg (91 %), colorless solid; 1 H-NMR (acetoned 6, 400 MHz): δ = 7.55 (d, 3 J = 8.72 Hz, 4H, Ar-H), 7.00 (s, 2H, Ar-H), 6.98 (d, 3 J = 8.82 Hz, 4H, Ar-H), (m, 2H, CHO), (m, 10H, CH 2 OH, CH 2 O), (m, 6H, CH 2 O, OH), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), (m, 6H, CH 2 ), (m, 24H, CH 2 ), 0.87 ppm (t, 3 J = 6.74 Hz, 3H, CH 3 ); 13 C-NMR (acetone-d 6, 125 MHz): δ = , (C-4,21), , (C-11,14), , (C- 9,16), (C-7,8,17,18), , (C-10,15), , (C-5,6,19,20), (C- 12,13), (C-2,23), 70.29, (C-3,22), 69.86, (CH 2 O), 64.10, (C-1,24), 32.53, 31.10, 30.93, 30.29, 30.26, 30.24, 30.21, 30.10, 30.02, 29.91, 29.72, 29.25, 26.75, 26.43, 23.22,

30 20.78 (CH 2 ), ppm (CH 3 ); 19 F-NMR (acetone-d 6, 188 MHz): δ = (t, 3 J = 9.91 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 14F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ) ppm (s, 2F, CF 2 CF 3 ); calculated for C 58 H 69 F 25 O 8 : C 50.88, H 5.08; found: C 50.65, H 5.37 %. 3-[4 -(2,3-Dihydroxypropoxy)-5 -decyloxy-2 -(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,- 15,15,16,16,16-henicosafluorohexadecyloxy)-p-terphenyl-4-yloxy]propane-1,2-diol (2a) Synthesized according to the general procedure from 9a (365 mg; 0.29 mmol); purified by crystallisation from MeOH. Yield: 273 mg (80 %), colorless solid; 1 H-NMR (CDCl 3, 400 MHz): δ = 7.48 (d, 3 J = 8.30 Hz, 4H, Ar-H), 6.91 (d, 3 J = 8.51 Hz, 4H, Ar-H), 6.88 (s, 2H, Ar-H), (m, 6H, CHO, CH 2 OH), (m, 6H, CH 2 O, OH), (m, 2H, CH 2 O), 2.40 (bs, 2H, OH), 2.25 (bs, 2H, OH), (m, 2H, CH 2 CF 2 ), (m, 4H, OCH 2 CH 2 ), (m, 2H, CH 2 CH 2 CF 2 ), (m, 18H, CH 2 ), 0.84 ppm (t, 3 J = 7.05 Hz, 3H, CH 3 ); 13 C-NMR (CDCl 3, 125 MHz): δ = , (C-4,21), , (C-11,14), , (C- 9,16), (C-7,8,17,18), , (C-10,15), , , (C-5,6,19,20), , (C-12,13), , (C-2,23), (C-3,22), 69.37, (CH 2 O), 63.53, (C-1,24), 31.82, 30.90, 30.72, 30.54, 29.50, 29.46, 29.27, 29.24, 29.20, 29.03, 28.67, 25.97, 25.71, 22.58, (CH 2 ), ppm (CH 3 ); 19 F-NMR (CDCl 3, 188 MHz): δ = (t, 3 J = 9.91 Hz, 3F, CF 3 ), (s, 2F, CH 2 CF 2 ), (s, 10F, CF 2 ), (s, 2F, CF 2 ), (s, 2F, CF 2 ) ppm (s, 2F, CF 2 CF 3 ); calculated for C 50 H 57 F 21 O 8 : C 50.68, H 4.85; found: C 50.37, H 5.17 %.

31 Supplementary References 38. Immirzi, A. & Perini, B. Prediction of density in organic crystals. Acta Cryst. A 33, (1977). 39. Amini, A., Bates, K., Benniston, A. C., Lawrie, D. J. & Soubeyrand-Lenoir, E. Towards molecular T-junction relays. Tetrahedron Lett. 44, (2003). 40. Ravindranath, R., Ajikumar, P. K., Advincula, R. C., Knoll, W. & Valiyaveettil, S. Fabrication and characterization of multilayer films from amphiphilic poly(p-phenylene)s. Langmuir 22, (2006). 41. Kölbel, M. et al. Design of liquid crystalline block molecules with nonconventional mesophase morphologies: calamitic bolaamphiphiles with lateral alkyl chains. J. Am. Chem. Soc. 123, (2001). 42. Johansson, G., Percec, V., Ungar, G. & Zhou, J. P. Fluorophobic effect in the self-assembly of polymers and model compounds containing tapered groups into supramolecular columns. Macromolecules 29, (1996). 43. Hopken, J., Möller, M & Boileau, S. Self-organization of amphiphilic fluorocarbonhydrocarbon molecules. I. synthesis and interfacial activity of allyl ethers. New Polymeric Materials 2, (1991). 44. Broniatowski, M. & Dynarowicz-Łątka, P. Semifluorinated alcohols in Langmuir monolayers a comparative study. J. Col. Interf, Sci. 301, (2006).