Supplementary Figure 1. Synthetic route for the preparation of promesogeenic ligand. iii

Transcription

1 Supplementary Figure 1. Synthetic route for the preparation of promesogenic ligand. (i) 2,2,2- trichloroethanol, NaHCO 3 (ii) 1-bromohexadecane, K2CO 2 3, KI, DMF; D (iii) a.. KOH/EtOH, rfx; b. (COCl) 2, toluene, rfx; iv) KOH/EtOH, rfx; (iv) 1, DMAP, TEA, THF; (v) a. b. (COCl) 2, toluene, rfx c. resorcinol, TEA, THF, DMAP, room temp.,, 4 5 h; (vi) 16-mercaptohexadecanoic acid, DCC, THF, DMAP.

2 Supplementary Figure 2. X-ray photoelectron spectroscopy (XPS) survey analysis (a) XPS analysis of dodecanethiol-coated 12 2H 25 SH) and (b) hybridd silver nanoparticles silicone signal comes from the substrate. The quantative elemental analysis was performed in analogy to the previously described systems [Supplementary Refs 1, 2]. For this purposee the C/S atomic ratio calculated for the samples was used indicating that ca. 50% of the alkane ligands were exchanged to L molecules. The results are in good accordance to the values obtained from f TGA data.

3 Supplementary Figure 3. Diffraction patternn obtained for hybrid silver nanoparticles in wide angles; red curve is given for the eye guidance; peaks characteristic too Ag cubic structure weree found. Supplementary Figure 4. Thermogravimetric analysis of nanoparticles. (a) TGA analysis of dodecanethiol-coated 12 H 25 SH ) andd hybrid (Ag@L) silver nanoparticles; % of mass drops below and above 260 C are given in pictures. (b) Normalized derivative of TGA traces given in a).

4 Supplementary Figure 5. SAXRD analysis of a mechanically sheared Ag@L sample. Supplementary Figure 6. Optical characterization of Ag@C 12 H 2 5SH nanoparticles. max x position for a heated sample of dodecanethiol-coatedd silver nanoparticles (Ag@C 12 H 25 SH); no variation with temperature is observed.

5 Supplementary Figure 7. SAXRD analysis of sample after fast cooling. Cross section s of diffraction patterns obtained for hybrid (Ag@L) nanoparticles in a condensed state - dropcasted on the kapton foil, after fast (tens of seconds) cooling from 120 to 30 C (empty circles) ) as well as after slow cooling/heating cycle (blue and red r traces, respectively).

6 Supplementary Figure 8. NMR analysis of nanoparticles. (a) NMR analysis of a freshly prepared sample of Ag@L nanoparticles. (b) NMR analysis of the same s samplee after heating to 120 C. As previously described [Supplementaryy Ref. 1] NMR was usedd to confirm purity of the sample, i.e. that no unbound ligands are present in the sample. Before heating sharp signals coming from residual solvents are observed. After heating no sharp signals comingg from free ligands or solvents are observed confirming stability of the hybrid nanoparticles.

7 Supplementary Figure 9. Epsilon-near-zero (ENZ) properties of material ( enlarged region with eff 0). Theoretically predicted real (Re( eff f)) parts of the dielectricc function off Ag NPs aggregates in the Iso and Lm structure (red and blue traces, respectively) narrowed to the ENZ region as defined by Re( eff f) values in between -1 and 1; narrower region for Re( eff ) values in between -0.2 and 0.2 is indicated by the black rectangle. Supplementary Figure 10. Atomic force microscopic (AFM) of thin film. AFM measurements of thermally annealed Ag@LL film on alumina substrate were performed in an area in which a fine scratch was made to expose substrate. The image is colored c usingg height scale. A 1D height profile of a measurementt encompassing bare substrate and nanoparticle n film is given on the right. The mean height of the film is ca. 100 nm (between 95 and 1155 nm).

8 Supplementary Figure 11. Raw and fittedd spectroscopic ellipsometry data. (a) Amplitude (Psi), and (b) phase (Delta), of the complex reflectance ratio, recorded at 60, 65 and 70 incidence (violet, green and red for Psi respectively; black, blue, green for Delta, respectively). Corresponding modelling results are given in dark red. Details of the modelling aree given in Materials and methods section of the main text. Mean square error iss 1.1. Supplementary Figure 12. Optical properties of material exhibiting Lm phase. The complex refractive index (real - n and imaginary - k parts of refractive index, magneta and green trace, respectively) calculated based on ellipsometric measurements (complementary to o data at Fig. 4c in the main text).

9 Supplementary Figure 13. Imaginary (Im( eff )) and real (Re( eff ))) parts of the dielectric function of Ag NPs aggregates. (a) Calculated in the Lm structure with the reflection and transmission coefficients from calculations off an infinitelyy extended lattice and (b) an in house code introduced in [Supplementary Ref. 3] and the Clausius-Mo ssotti relation.

10 Supplementary Note 1 Details of promesogenic ligand synthesis (L) and analysis Synthesis of 2,2,2-trichloroethyl 4-hydroxybenzoate (1) 50.0 g (362.0 mmol) of 4-hydroxybenzoic acid in 500 ml of CH 2 Cl 2 and 100 ml of THF with the addition of 4.2 ml of DMF and 39.5 ml (543.0 mmol) of thionyl chloride were stirred at room temperature for 1 h. Next, ml ( mmol) of 2,2,2-trichloroethanol was added dropwise to the stirring mixture. Stirring was continued for 2 h. After that, 500 ml of saturated solution of NaHCO 3 was added to the stirring mixture. The organic phase was separated; the aqueous phase was extracted four-times using CHCl 3. All organic phases were combined, dried over anhydrous MgSO 4 and evaporated. The crude product was crystallized form cyclohexane affording pure product with 68% yield. Elemental analysis for C 9 H 7 Cl 3 O 3 (M ~ 269.5): calc. C 40.11, H 2.62, Cl 39.46, O 17.81; found C 40.91, H 2.91, Cl 38.99; 1 H NMR (200 MHz, CDCl 3, 25 C, TMS): δ = 7.83 (m, 2H; ArH), (m, 2H; ArH), 6.32 (br s; 1H; OH), 4.95 (s, 2H; CH 2 CCl 3 ); 13 C NMR (200 MHz, CDCl 3, 25 C, TMS): δ = , , , , , , 95.22, Synthesis of ethyl 4-hexadecyloxybenzoate (2) 80.0 g (481.9 mmol) of the ethyl ester of 4-hydroxybenzoic acid, 99.3 g (719.6 mmol) of K 2 CO 3, 95.6 g (576.5 mmol) of KI, ml (575.4 mmol) of 1-bromohexadecane and 1100 ml of DMF were put together in a round-bottom flask. Then, the reaction mixture was heated up and stirred for 10 h at C. The flask content was poured out into ice/water mixture, and extracted three times with with toluene. Combined extracts were dried using anhydrous MgSO 4, filtered and evaporated. The crude product was crystallized form ethanol affording pure product with 86% yield. Elemental analysis for C 25 H 42 O 3 (M ~ 390.6): calc. C 76.87, H 10.84, O 12.29; found C 77.1, H %; 1 H NMR (200 MHz, CDCl 3, 25 C, TMS): δ = (m, 2H; ArH), (m, 2H; ArH), 4.33 (t, J = 7.0 Hz, 2H; COOCH 2 ), 4.05 (t, J = 6.4 Hz, 2H; CH 2 O), (m, 2H;

11 CH 2 CH 2 O), (m, 29H), 0.88 (t, J = 6.5 Hz, 3H; CH 3 ); 13 C NMR (200 MHz, CDCl 3, 25 C, TMS): δ = , , , , , , 68.57, 61.08, 32.13, 29.89, 29.78, 29.57, 29.27, 26.18, 22.90, Synthesis of 4-(hexadecyloxy)benzoyl chloride ( mmol) of the ethyl ester of 4-hexadecylobenzoic acid was dissolved in 1476 ml of ethanol; then potassium hydroxide g, (2590 mmol) in ethanol (738 ml) was added. The reaction mixture was heated under reflux for 8 h after which it was left to cool to room temperature. White precipitate formed throughout the course of the reaction which was filtered, washed with copious amounts of ethanol and dried under vacuum, yielding potassium salt of 4-hexadecylobenzoic acid. Excess of oxalyl chloride (20.0 ml) was added dropwise to a solution of potassium salt of 4- hexadecylobenzoic acid (20.00 g, 50.0 mmol) in dry toluene and the mixture was heated under reflux for 6h. After filtration of the precipitated potassium chloride, the filtrate was evaporated to dryness affording product with 94% yield. Synthesis of 4-[(2,2,2-trichloroethoxy)carbonyl]phenyl-4-(hexadecyloxy)benzoate (3) TEA (53 ml) was added to the solution of 1 (10.51 g, 38.9 mmol) and DMAP (catalytic amount) in 370 ml of THF. Then, chloric acid of 4-hexadecylobenzoic acid (17.8 g, 46.8 mmol) in 100 ml of THF was added dropwise. The reaction mixture was stirred for 8 h at reflux. A precipitate of triethylamine hydrochloride formed which was filtered and the filtrate was evaporated to dryness. The crude product was chromatographed on silica gel eluted with dichloromethane affording pure product with 90% yield. Elemental analysis for C 32 H 43 Cl 3 O 5 (M ~ 614.0): calc. C 62.59, H 7.06, Cl 17.32, O %; found C 63.01, H 7.16, Cl %; 1 H NMR (200 MHz, CDCl 3, 25 C, TMS): δ = (m, 4H; ArH), (m, 2H; ArH), (m, 2H; ArH), 4.99 (s, 2H; CH 2 CCl 3 ), 4.05 (t, J = 6.4 Hz, 2H; CH 2 O), (m, 2H; CH 2 CH 2 O), (m, 26H), 0.88 (t, J = 6.5 Hz, 3H; CH 3 ); 13 C NMR (200 MHz, CDCl 3, 25 C, TMS): δ = , , , , , , , , , 95.22, 74.67, 68.57, 32.12, 29.88, 29.78, 29.56, 29.27, 26.17, 22.89, Synthesis of 4-[(3-hydroxyphenoxy)carbonyl]phenyl-4-(hexadecyloxy)benzoate (4)

12 16.88 g (27.51 mmol) of 4-[(2,2,2-trichloroethoxy)carbonyl]phenyl- 4-(hexadecyloxy)benzoate, 300 ml of THF, 15.5 g of Zn and 60 ml of CH 3 COOH were stirred at room temperature for 6 h. Inorganic precipitate was filtered out, 600 ml of toluene was added to the mixture and evaporated to dryness (to remove CH 3 COOH) yielding crude product. The obtained Zn salt was washed with hexane. In next step g (16.2) of Zn salt with 600 ml of toluene and 15 ml of oxalyl chloride was heated under reflux for 6h. Inorganic substances were filtered affording 4-(chlorocarbonyl)phenyl-4- (hexadecyloxy)benzoate (13.8 g). In the next step, TEA (13.8 ml) was added to the solution of resorcinol (45.5 g, mmol) and DMAP (catalytic amount) in 300 ml of THF. Then, 4-(chlorocarbonyl)phenyl-4- (hexadecyloxy)benzoate (13.8 g, mmol) in 100 ml of THF was added. The reaction mixture was stirred for 8 h at reflux and evaporated to dryness. The crude product was crystallized from methanol twice, affording pure product with 40% yield. Elemental analysis for C 36 H 46 O 6 (M ~ 574.7): calc. C 75.23, H 8.07, O 16.70; found C 75.45, H 8.17%; 1 H NMR (500 MHz, CDCl 3, 25 C, TMS): δ = (m, 2H; ArH), (d, 2H; ArH), (m, 2H; ArH), (m, 1H; ArH), (m, 2H; ArH), (m, 1H; ArH), (m, 2H; ArH), 5.30 (br s, 1H; OH), 4.05 (t, J = 6.5 Hz, 2H; CH 2 O), (m, 2H; CH 2 CH 2 O), (m, 2H; CH 2 CH 2 CH 2 O), (m, 24H), 0.88 (3H, t, J = 7.0 Hz; CH 3 ); 13 C NMR (500 MHz, CDCl 3, 25 C, TMS): δ = , , , , , , , , , , , , , , , , 68.42, 31.94, 29.71, 29.70, 29.68, 29.61, 29.57, 29.38, 29.10, 25.99, 22.71, Synthesis of 4-({4-[(16-sulfanylhexadecanoyl)oxy]phenoxy}carbonyl)phenyl-4- (hexadecyloxy)benzoate (5) DCC (206 mg, 1.05 mmol) was added to the solution of 4 (575 mg, 1.0 mmol), DMAP (catalytic amount) in 20 ml of dichloromethane at room temperature and stirred for 12h. A white precipitate formed which was fileterd out. The crude product was chromatographed twice on silica gel eluted with toluene affording pure product with 15% yield.

13 Elemental analysis for C 52 H 76 O 7 S (M ~ 845.2): calc. C 73.89, H 9.06, O 13.25, S 3.79; found C 74.07, H 9.16, S 3.88; 1 H NMR (500 MHz, CDCl 3, 25 C, TMS): δ = (m, 2H; ArH), (m, 2H; ArH), 7.43 (t, J = 8.0 Hz, 1H; ArH), (m, 2 H; ArH), (m, 1H; ArH), (m, 2H; ArH), (m, 2H; ArH), 4.05 (t, J = 7.0 Hz, 2H), 2.56 (t, J = 7.5 Hz, 2H; CH 2 COO), 2.52 (q, J = 7.0 Hz, 2H; CH 2 S), (m, 2H; CH 2 CH 2 O), (m, 53H), 0.88 (t, J = 7.0 Hz, 3H; CH 3 ); 13 C NMR (500 MHz, CDCl 3, 25 C, TMS): δ = , , , , , , , , , , , , , , , , , 45.21, 34.38, 34.08, 32.66, 31.93, 29.70, 29.68, 29.67, 29.63, 29.61, 29.56, 29.47, 29.40, 29.37, 29.34, 29.10, 28.90, 28.77, 28.19, 26.90, 25.98, 24.89, 22.70, Supplementary References 1. Lewandowski, W. et al. Smectic mesophases of functionalized silver and gold nanoparticles with anisotropic plasmonic properties. Chem. Commun. 49, (2013). 2. Lewandowski, W., Jatczak, K., Pociecha, D. & Mieczkowski, J. Control of gold nanoparticle superlattice properties via mesogenic ligand architecture. Langmuir 29, (2013). 3. Mühlig S., Rockstuhl C., Pniewski J., Simovski C. R., Tretyakov S. A., Lederer F., Phys. Rev. B 81, (2010).