Supporting Information for Induction of Thermotropic Bicontinuous Cubic Phases in Liquid-Crystalline Ammonium and Phosphonium Salts Takahiro Ichikawa,, Masafumi Yoshio, Atsushi Hamasaki, Satomi Taguchi, Feng Liu, Xiang-bing Zeng, Goran Ungar,,# Hiroyuki Ohno, and Takashi Kato *, The University of Tokyo, Tokyo University of Agriculture and Technology, T University of Sheffield, # Seoul National University Contents 1. General Procedures and Materials.. S2 2. Synthesis....S3-S11 3. POM, DSC and XRD, and Elemental Analysis on Individual Compounds 3.1 Compounds 1(n/BF 4 )......... S12-S14 3.2 Compounds 2(n/BF 4 )....... S15-S17 3.3 Compounds 3(n/BF 4 )........ S18-S20 3.4 Compounds 4(n/BF 4 )........ S21-S23 3.5 Compounds 5(n/BF 4 )......... S24-S26 3.6 Compounds6(n/BF 4 ).......S27-S29 3.7 Compounds 2(n/PF 6 )....... S30-S32 3.8 Compounds 2(n/CF 3 SO 3 ).........S33 3.9 Mixture of Compound 5(10/BF 4 ) and LiBF 4.........S34 4. Synchrotron XRD Data used in the Construction of Electron Density Maps..S35-S36 5. Construction of Differential Electron Density Maps...S38-S39 S1
1. General Procedures and Materials General Procedures. 1 H NMR and 13 C NMR spectra were obtained on a JEOL JNM-LA400 at 400 and 100 MHz in CDCl 3, respectively. Chemical shifts of 1 H and 13 C NMR signals were quoted to (CH 3 ) 4 Si (δ = 0.00) and CDCl 3 (δ = 77.0) as internal standards, respectively. Elemental analyses were carried out on a Yanaco MT-6 CHN autocorder and an Exeter Analytical CE440 instrument. The thermal properties of the materials were examined by a DSC using a Netzsch DSC204 Phoenix. The heating and cooling rates were 10 C min -1. Transition temperatures were taken at the onset of the transition peaks. A polarizing optical microscope Olympus BX51 equipped with a Mettler FP82HT hot stage was used for visual observation. Wide-angle X-ray diffraction (WAXD) patterns were obtained using a Rigaku RINT-2500 diffractometer with Cu K radiation. Two-dimensional small-angle X-ray scattering (2D SAXS) patterns of the materials were also recorded using an image plate detector (R-AXIS DS3C). High-resolution small-angle powder diffraction experiments were performed at Station I22 of the Diamond Light Source synchrotron, U.K. Materials. All chemical reagents and solvents were obtained from commercial sources and used without purification. All reactions were carried out under an argon atmosphere in anhydrous solvents. Measurement of Ionic Conductivities. Temperature dependence of the ionic conductivities was measured in the heating process by the alternating current impedance method using a Schlumberger Solartron 1260 impedance analyzer (frequency range: 10 Hz-10 MHz, applied voltage: 0.3 V) equipped with a temperature controller. The cooling rate was fixed to 2 K min 1. Ionic conductivities were practically calculated to be the product of 1/R b (Ω 1 ) times cell constants (cm 1 ) of the comb-shaped gold electrodes, which were calibrated with KCl aqueous solution (1.00 mmol L 1 ) as a standard conductive solution. The impedance data (Z) were modeled as a connection of two RC circuits in series. S2
2. Synthesis Synthesis of trimethyl (or triethyl, or trypropyl)-[3,4,5-tris(alkyloxy)benzyl]ammonium tetrafluoroborates 1(n/BF 4 ), 2(n/BF 4 ), and 3(n/BF 4 ). The synthetic pathways used to obtain compounds 1-3(n/BF 4 ), are shown in Scheme S1. Methyl-3,4,5-trihydroxybenzoate was etherified with 1-bromoalkane (CH 3 (CH 2 ) n-1 Br, n: carbon number of alkyl chain) in the presence of potassium carbonate (K 2 CO 3 ) in N,N-dimethylformamide (DMF) to yield methyl-3,4,5-tris(alkyloxy)benzoates 7(n). After reduction of the esters 7(n) with lithium aluminium hydride (LiAlH 4 ) in tetrahydrofuran (THF), the resulting benzyl alcohols 8(n) were converted to 3,4,5-tris(alkyloxy)benzyl chlorides 9(n) with thionyl chloride (SOCl 2 ) in dichloromethane (CH 2 Cl 2 ). Subsequent quarternalization reaction of trimethyl (or triethyl, or trypropyl) amine with compounds 9(n) in toluene gave ammonium chlorides 1-3(n/Cl). Finally, ammonium tetrafluoroborates 1-3(n/BF 4 ) were prepared by the anion exchange reaction of the corresponding ammonium chlorides 1-3(n/Cl) with silver tetrafluoroborate (AgBF 4 ) in methanol (MeOH). Scheme S1. Synthesis of wedge-shaped ammonium salts 1-3(n/BF 4 ) Synthesis of trimethyl (or triethyl, or trypropyl)-[3,4,5-tris(alkyloxy)benzyl]phosphonium tetrafluoroborates 4(n/BF 4 ), 5(n/BF 4 ), and 6(n/BF 4 ). The synthetic pathways used to obtain compounds 4-6(n/BF 4 ), are shown in Scheme S2. S3
Compounds 8(n) were converted to 3,4,5-tris(alkyloxy)benzyl bromides 10(n) with phosphorous tribromide (PBr 3 ) in dichloromethane (CH 2 Cl 2 ). Subsequent quarternalization reaction of trimethyl (or triethyl, or trypropyl) phosphine with compounds 10(n) in THF gave phosphonium bromides 4-6(n/Cl). Finally, phosphonium tetrafluoroborates 4-6(n/BF 4 ) were prepared by the anion exchange reaction of the corresponding phosphonium chlorides 4-6(n/Cl) with silver tetrafluoroborate (AgBF 4 ) in methanol (MeOH). Synthesis of compounds 4-6(10/BF 4 ) are shown below. Scheme S2. Synthesis of wedge -shaped phosphonium salts 4-6(n/BF 4 ) Synthesis of triethyl-[3,4,5-tris(alkyloxy)benzyl]ammonium hexafluorophosphate 2(n/PF 6 ) and ammonium trifluoromethanesulfonate 2(n/CF 3 SO 3 ). The synthetic pathways used to obtain compounds 2(n/PF 6 ) and 2(n/CF 3 SO 3 ) are shown in Scheme S3. Compounds 2(n/PF 6 ) and 2(n/CF 3 SO 3 ) were prepared by the anion exchange reaction of the corresponding ammonium chlorides 2(n/Cl) with lithium hexafluorophosphate and lithium trifluoromethanesulfonate in methanol (MeOH). Scheme S3. Synthesis of wedge-shaped ammonium salts 2(n/PF 6 ) and 2(n/CF 3 SO 3 ) S4
Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride To a solution of 3,4,5-tris(dodecyloxy)benzyl chloride (2.00 g, 2.94 mmol) in toluene (10 ml) was added a solution of trimethyllammine (0.87 g, 14.7 mmol) in toluene (10 ml) with stirring at room temperature. The solution was heated and stirred at 90 C for 12 h. The reaction mixture was extracted three times with CHCl 3 and washed with a 5 % HCl aqueous solution. The resulting organic phase was dried over anhydrous MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 /methanol = 10/1) to give Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride 1.99 g (88 %) as a white solid. 1 H NMR (400 MHz): δ = 6.75 (s, 2 H), 4.73 (s, 2H), 3.98 (m, 6 H), 3.49 (q, J = 7.3 Hz, 6 H), 1.82-1.70 (m, 6H), 1.47-1.26 (m, 63 H), 0.88 (t, J = 6.8 Hz, 9 H). 13 C NMR (100 MHz): δ =153.07, 139.61, 121.60, 110.69, 73.14, 69.14, 61.27, 52.45, 31.57, 30.00, 29.40, 29.30, 29.25, 29.14, 29.01, 25.80, 25.74, 22.32, 13.75, 8.08. Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium tetrafluoroborate To a solution of Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (1.00 g, 1.30 mmol) in MeOH (3 ml) under argon was added a solution of AgBF 4 (0.304 g, 1.56 mmol) in MeOH (2 ml) with stirring at room temperature. The mixture was stirred at room temperature for 2 h. An insoluble AgCl was filtered off through a pad of celite by using a suction funnel. The filtrate was concentrated under reduced pressure. The crude product was purified by flash-column chromatography on silica gel (silica gel, eluent: CH 2 Cl 2 /MeOH = 10/1) to give 1.02 g (96 %) of the pure product as a white solid. 1 H NMR (400MHz): δ = 6.61 (s, 2 H), 4.34 (s, 2H), 3.97 (m, 6 H), 3.28 (q, J = 7.3 Hz, 6 H), 1.82-1.70 (m, 6H), 1.57-1.26 (m, 63 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.46, 139.89, 121.57, 110.62, 73.42, 69.30, 52.53, 31.88, 30.34, 29.71, 29.69, 29.65, 29.63, 29.57, 29.48, 29.37, 29.32, 26.12, 26.06, 26.01, 22.63, 14.03, 7.66. S5
Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride. To a solution of 3,4,5-tris(dodecyloxy)benzyl chloride (2.00 g, 2.94 mmol) in toluene (10 ml) was added a solution of triethyllammine (1.49 g, 14.7 mmol) in toluene (10 ml) with stirring at room temperature. The solution was heated and stirred at 90 C for 6 h. The reaction mixture was extracted three times with CHCl 3 and washed with a 5 % HCl aqueous solution. The resulting organic phase was dried over anhydrous MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (2.04 g, 85 %) as a white solid. 1 H NMR (400 MHz): δ = 6.75 (s, 2 H), 4.73 (s, 2H), 3.98 (m, 6 H), 3.49 (q, J = 7.3 Hz, 6 H), 1.82-1.70 (m, 6H), 1.47-1.26 (m, 63 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ =153.07, 139.61, 121.60, 110.69, 73.14, 69.14, 61.27, 52.45, 31.57, 30.00, 29.40, 29.30, 29.25, 29.14, 29.01, 25.80, 25.74, 22.32, 13.75, 8.08. Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium tetrafluoroborate To a solution of Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (1.00 g, 1.23 mmol) in MeOH (3 ml) under argon was added a solution of AgBF 4 (0.288 g, 1.48 mmol) in MeOH (2 ml) with stirring at room temperature. The mixture was stirred at room temperature for 2 h. An insoluble AgCl was filtered off through a pad of celite by using a suction funnel. The filtrate was concentrated under reduced pressure. The crude product was purified by flash-column chromatography on silica gel (silica gel, eluent: CH 2 Cl 2 /MeOH = 10 : 1) to give 1.00 g (94 %) of the pure product as a white solid. 1 H NMR (400MHz): δ = 6.61 (s, 2 H), 4.34 (s, 2H), 3.97 (m, 6 H), 3.28 (q, J = 7.3 Hz, 6 H), 1.82-1.70 (m, 6H), 1.57-1.26 (m, 63 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.46, 139.89, 121.57, 110.62, 73.42, 69.30, 52.53, 31.88, 30.34, 29.71, 29.69, 29.65, 29.63, 29.57, 29.48, 29.37, 29.32, 26.12, 26.06, 26.01, 22.63, 14.03, 7.66. S6
Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride To a solution of 3,4,5-tris(dodecyloxy)benzyl chloride (2.00 g, 2.94 mmol) in toluene (10 ml) was added a solution of tripropylammine (2.11 g, 14.7 mmol) in toluene (10 ml) with stirring at room temperature. The solution was heated and stirred at 90 C for 6 h. The reaction mixture was extracted three times with CHCl 3 and washed with a 5 % HCl aqueous solution. The resulting organic phase was dried over anhydrous MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (1.56 g, 62 %) as a white solid. 1 H NMR (400 MHz): δ = 6.72 (s, 2 H), 4.84 (s, 2H), 3.97 (m, 6 H), 3.29 (m, 6 H), 1.82-1.26 (m, 66 H), 1.02 (t, J = 6.8 Hz, 9 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.54, 140.10, 121.96 110.98, 73.51, 69.54, 59.91, 31.89, 30.30, 30.00, 29.72, 29.68, 29.64, 29.62, 29.57, 29.40, 29.34, 26.09, 26.05, 22.66, 16.21, 14.09, 10.80. Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium tetrafluoroborate To a solution of Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (1.00 g, 1.17 mmol) in MeOH (3 ml) under argon was added a solution of AgBF 4 (0.274 g, 1.41 mmol) in MeOH (2 ml) with stirring at room temperature. The mixture was stirred at room temperature for 2 h. An insoluble AgCl was filtered off through a pad of celite by using a suction funnel. The filtrate was concentrated under reduced pressure. The crude product was purified by flash-column chromatography on silica gel (silica gel, eluent: CH 2 Cl 2 /MeOH = 10 : 1) to give 0.96 g (91 %) of the pure product as a white solid. 1 H NMR (400 MHz): δ = 6.58 (s, 2 H), 4.39 (s, 2H), 3.95 (m, 6 H), 3.09 (t, J = 6.4 Hz, 6 H), 1.81-1.26 (m, 66 H), 0.98 (t, J = 7.2 Hz, 9 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.58, 140.00, 121.50 110.48, 73.49, 69.34, 6314, 59.77, 31.93, 31.91, 30.34, 29.76, 29.71, 29.69, 29.65, 29.60, 29.45, 29.39, 29.36, 26.10, 26.08, 22.68, 15.76, 14.11, 10.56. S7
Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide To a solution of 3,4,5-tris(dodecyloxy)benzyl bromide (2.00 g, 3.13 mmol) in tetrahydrofuran (10 ml) was added a solution of trimethylphosphine (1.19 g, 15.7 mmol) in tetrahydrofuran (10 ml) with stirring at room temperature. The solution was heated and stirred at 90 C for 6 h. The reaction mixture was extracted three times with CHCl 3 and washed with sat. NaCl aq., dried over MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide (1.92 g, 86 %) as a white solid. 1 H NMR (400 MHz): δ = 6.58 (d, J = 2.4 Hz, 2 H), 4.15 (d, J = 15.6 Hz, 2H), 3.94 (m, 6 H), 2.15 (d, J = 14.4 Hz, 9 H), 1.82-1.70 (m, 6H), 1.46-1.27 (m, 42 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ =153.70, 138.09, 122.90, 108.22, 73.38, 69.38, 31.87, 30.30, 29.70, 29.63, 29.60, 29.55, 29.43, 29.36, 29.32, 26.11, 26.06, 22.64, 14.08, 8.94, 8.40. Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium tetrafluoroborate To a solution of Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide (1.00 g, 1.40 mmol) in MeOH (5 ml) was added a solution of AgBF 4 (0.326 g, 1.68 mmol) in MeOH (3 ml) with stirring at room temperature for 1 h. An insoluble AgCl was filtered off through a pad of celite by using a suction funnel. The filtrate was concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Trimethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium tetrafluoroborate (0.98 g, 91 %) as a white solid. 1 H NMR (400 MHz): δ = 6.46 (d, J = 2.4 Hz, 2 H), 3.93 (m, 6 H), 3.59 (d, J = 15.6 Hz, 2H), 1.84 (d, J = 14.0 Hz, 9 H), 1.80-1.70 (m, 6H), 1.47-1.26 (m, 42 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.81, 138.08, 122.58, 107.99, 73.43, 69.25, 31.91, 30.33, 30.14, 29.74, 29.68, 29.64, 29.59, 29.48, 29.36, 26.13, 26.10, 22.68, 14.11, 7.69, 7.14. S8
Triethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide To a solution of 3,4,5-tris(dodecyloxy)benzyl bromide (2.00 g, 3.13 mmol) in tetrahydrofuran (10 ml) was added a solution of triethylphosphine (1.85 g, 15.7 mmol) in tetrahydrofuran (10 ml) with stirring at room temperature. The solution was heated and stirred at 90 C for 6 h. The reaction mixture was extracted three times with CHCl 3 and washed with sat. NaCl aq., dried over MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Triethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide (1.88 g, 79 %) as a white solid. 1 H NMR (400 MHz): δ = 6.70 (d, J = 2.4 Hz, 2H), 4.16 (d, J = 14.8 Hz, 2H), 3.95 (m, 6H), 2.50 (q, 6H), 1.82-1.70 (m, 6H), 1.46-1.27 (m, 51H), 0.89 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.66, 122.83, 108.40, 73.35, 69.40, 31.83, 30.24, 29.66, 29.57, 29.52, 29.42, 29.34, 29.28, 26.08, 26.03, 22.60, 14.03, 12.30, 11.82, 6.01, 5.96. Triethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium tetrafluoroborate To a solution of Triethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide (1.01 g, 1.32 mmol) in MeOH (5 ml) was added a solution of AgBF 4 (0.308 g, 1.58 mmol) in MeOH (3 ml) with stirring at room temperature for 1 h. An insoluble AgCl was filtered off through a pad of celite by using a suction funnel. The filtrate was concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Triethyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium tetrafluoroborate (1.01 g, 95 %) as a white solid. 1 H NMR (400 MHz): δ = 6.51 (d, J = 2.4 Hz, 2 H), 3.95 (m, 6 H), 3.61 (d, J = 14.8 Hz, 2H), 2.21 (m, 6 H), 1.82-1.70 (m, 6H), 1.46-1.27 (m, 51 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.76, 138.00, 122.51, 108.00, 73.37, 69.23, 31.89, 31.88, 30.30, 29.71, 29.65, 29.62, 29.57, 29.48, 29.36, 29.33, 26.10, 26.08, 22.65, 14.07, 11.62, 11.14, 5.54, 5.48. S9
Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide To a solution of 3,4,5-tris(dodecyloxy)benzyl bromide (2.00 g, 3.13 mmol) in tetrahydrofuran (10 ml) was added a solution of tripropylphosphine (2.50 g, 1.57 mmol) in tetrahydrofuran (10 ml) with stirring at room temperature. The solution was heated and stirred at 90 C for 6 h. The reaction mixture was extracted three times with CHCl 3 and washed with sat. NaCl aq., dried over MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide (1.78 g, 71 %) as a white solid. 1 H NMR (400 MHz): δ = 6.68 (d, J = 2.4 Hz, 2 H), 4.22 (d, J = 14.8 Hz, 2H), 3.95 (m, 6 H), 2.38 (m, 6H), 1.80-1.70 (m, 6H), 1.47-1.26 (m, 48 H), 1.07 (t, J = 7.2 Hz, 9 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ =153.65, 137.94, 123.04, 108.29, 73.34, 69.37, 31.84, 30.23, 29.68, 29.61, 29.57, 29.53, 29.38, 29.31, 29.29, 27.28, 26.08, 26.03, 22.61, 21.15, 20.70, 15.71, 15.65, 15.50, 14.04. Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium tetrafluoroborate To a solution of Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium bromide (1.00 g, 1.25 mmol)in MeOH (5 ml) was added a solution of AgBF 4 (0.292 g, 1.50 mmol) in MeOH (3 ml) with stirring at room temperature for 1 h. An insoluble AgCl was filtered off through a pad of celite by using a suction funnel. The filtrate was concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, eluent CH 2 Cl 2 / methanol = 10/1) to give Tripropyl-[3,4,5-tris(dodecyloxy)benzyl]phosphonium tetrafluoroborate (0.96 g, 90 %) as a white solid. 1 H NMR (400 MHz): δ = 6.49 (d, J = 2.0 Hz, 2 H), 3.93 (m, 6 H), 3.62 (d, J = 14.0 Hz, 2H), 2.11 (m, 6 H), 1.81-1.69 (m, 6H), 1.52-1.26 (m, 48 H), 1.05 (t, J = 7.2 Hz, 9 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.81, 137.99, 122.57, 107.93, 73.40, 69.25, 31.90, 30.31, 29.74, 29.68, 29.63, 29.60, 29.45, 29.39, 29.36, 26.57, 26.10, 22.67, 20.66, 20.20, 15.59, 15.48, 15.42, 14.10. S10
Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium hexafluorophosphate To a solution of Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (1.00 g, 1.23 mmol) in MeOH (5 ml) under argon was added a solution of LiPF 6 (0.932 g, 6.15 mmol) in MeOH (20 ml) with stirring at room temperature. The mixture was stirred at room temperature for 24 h. The reaction mixture was extracted three times with CHCl 3 and washed with water, dried over MgSO 4, filtered through a pad of celite, and concentrated under reduced pressure. The crude product was purified by flash-column chromatography on silica gel (silica gel, eluent: CH 2 Cl 2 /MeOH = 10 : 1) to give 0.78 g (60 %) of the pure product as a white solid. 1 H NMR (400MHz): δ = 6.60 (s, 2 H), 4.34 (s, 2H), 3.97 (m, 6 H), 3.29 (q, J = 7.3 Hz, 6 H), 1.81-1.72 (m, 6H), 1.57-1.27 (m, 63 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 153.34, 139.75, 121.62, 110.73, 73.55, 69.24, 52.60, 31.89, 30.35, 29.70, 29.68, 29.64, 29.61, 29.57, 29.50, 29.41, 29.35, 26.24, 26.18, 26.12, 22.44, 13.68, 7.76. Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium trifluoromethanesulfonate To a solution of Triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium chloride (1.00 g, 1.23 mmol) in MeOH (5 ml) under argon was added a solution of LiCF 3 SO 3 (0.959 g, 6.15 mmol) in MeOH (20 ml) with stirring at room temperature. The mixture was stirred at room temperature for 24 h. The reaction mixture was extracted three times with CHCl 3 and washed with water, dried over MgSO 4, filtered through a pad of Celite, and concentrated under reduced pressure. The crude product was purified by flash-column chromatography on silica gel (silica gel, eluent: CH 2 Cl 2 /MeOH = 10 : 1) to give 0.72 g (55 %) of the pure product as a white solid. 1 H NMR (400MHz): δ = 6.62 (s, 2 H), 4.40 (s, 2H), 3.97 (m, 6 H), 3.32 (q, J = 7.3 Hz, 6 H), 1.80-1.72 (m, 6H), 1.56-1.26 (m, 63 H), 0.88 (t, J = 6.8 Hz, 9H). 13 C NMR (100 MHz): δ = 152.56, 139.50, 121.68, 110.77, 73.52, 69.52, 52.63, 31.92, 31.14, 29.73, 29.70, 29.67, 29.65, 29.57, 29.50, 29.36, 29.34, 26.15, 26.09, 26.02, 22.65, 13.53, 7.77. S11
3. POM, DSC, XRD, and Elemental Analysis Data on Individual Compounds 3.1. POM, DSC, XRD, and Elemental Analysis Data on Compounds 1(n/BF 4 ) N BF4 1(10/BF 4 ) Elemental analysis calcd (%) for C 40 H 76 BF 4 NO 3 : C, 68.06; H, 10.85; N, 1.98. Found: C, 67.87; H, 11.05; N, 1.86. Figure S1. Polarizing optical microscopic image of 1(10/BF 4 ) in the Col h phase at 150 C. Figure S2. DSC thermograms of 1(10/BF 4 ). Figure S3. Wide-angle X-ray diffraction pattern of 1(10/BF 4 ) in the Col h phase at 100 C. S12
C 12 H 25 O C 12 H 25 O C 12 H 25 O N BF4 1(12/BF 4 ) Elemental analysis calcd (%) for C 46 H 88 BF 4 NO 3 : C, 69.94; H, 11.23; N, 1.77. Found: C, 69.77; H, 11.51; N, 1.60. Figure S4. Polarizing optical microscopic image of 1(12/BF 4 ) in the Col h phase at 200 C. Figure S5. DSC thermograms of 1(12/BF 4 ). Figure S6. Wide-angle X-ray diffraction pattern of 1(12/BF 4 ) in the Col h phase at 150 C. S13
C 14 H 29 O C 14 H 29 O C 14 H 29 O N BF4 1(14/BF 4 ) Elemental analysis calcd (%) for C 52 H 100 BF 4 NO 3 : C, 71.45; H, 11.53; N, 1.60. Found: C, 71.23; H, 11.81; N, 1.47. Figure S7. Polarizing optical microscopic image of 1(14/BF 4 ) in the Col h phase at 192 C. Figure S8. DSC thermograms of 1(14/BF 4 ). Figure S9. Wide-angle X-ray diffraction pattern of 1(14/BF 4 ) in the Col h phase at 100 C. S14
3.2. POM, DSC, XRD, and Elemental Analysis Data on Compounds 2(n/BF 4 ) N BF 4 2(10/BF 4 ) Elemental analysis calcd (%) for C 43 H 82 BF 4 NO 3 : C, 69.05; H, 11.05; N, 1.87. Found: C, 68.88; H, 11.16; N, 1.81. Figure S10. Polarizing optical microscopic image of 2(10/BF 4 ) in the Cub bi phase at 50 C. Figure S11. DSC thermograms of 2(10/BF 4 ). Figure S12. Wide-angle X-ray diffraction patterns of 2(10/BF 4 ) at 50 C in the Cub bi phase. S15
C 12 H 25 O C 12 H 25 O C 12 H 25 O N BF 4 2(12/BF 4 ) Elemental analysis calcd (%) for C 49 H 94 BF 4 NO 3 : C, 70.73; H, 11.39; N, 1.68. Found: C, 70.65; H, 11.50; N, 1.60. Figure S13. Polarizong optical microscopic images of 2(12/BF 4 ): (a) in the Cub bi phase at 45 C and (b) in the Col h phase at 110 C. Figure S14. DSC thermograms of 2(12/BF 4 ). Figure S15. (a) Wide-angle X-ray diffraction pattern of 2(12/BF 4 ) in the Col h phase at 120 C; (b) Small-angle X-ray scattering pattern 2(12/BF 4 ) in the Cub bi phase at 45 C. S16
C 14 H 29 O C 14 H 29 O C 14 H 29 O 2(14/BF 4 ) N BF 4 Elemental analysis calcd (%) for C 55 H 106 BF 4 NO 3 : C, 72.10; H, 11.66; N, 1.53. Found: C, 71.91; H, 11.82; N, 1.46. Figure S16. Polarizing optical microscopic image of 2(14/BF 4 ) in the Col h phase at 110 C. Figure S17. DSC thermograms of 2(14/BF 4 ). Figure S18. Wide-angle X-ray diffraction pattern of 2(14/BF 4 ) in the Col h phase at 110 C. S17
3.3. POM, DSC, XRD, and Elemental Analysis Data on Compounds 3(n/BF 4 ) 3(10/BF 4 ) N BF 4 Elemental analysis calcd (%) for C 46 H 88 BF 4 NO 3 : C, 69.94; H, 11.23; N, 1.77. Found: C, 69.85; H, 11.50; N, 1.72. Figure S19. DSC thermograms of 3(10/BF 4 ). S18
C 12 H 25 O C 12 H 25 O C 12 H 25 O N BF 4 3(12/BF 4 ) Elemental analysis calcd (%) for C 52 H 100 BF 4 NO 3 : C, 71.45; H, 11.53; N, 1.60. Found: C, 71.27; H, 11.77; N, 1.46. Figure S20. DSC thermograms of 3(12/BF 4 ). S19
C 14 H 29 O C 14 H 29 O C 14 H 29 O 3(14/BF 4 ) N BF 4 Elemental analysis calcd (%) for C 58 H 112 BF 4 NO 3 : C, 72.69; H, 11.78; N, 1.46. Found: C, 72.50; H, 12.00; N, 1.30. Figure S21. Polarizing optical microscopic images of 3(14/BF 4 ) in the Col h phase at 80 C. Figure S22. DSC thermograms of 3(14/BF 4 ). Figure S23. Wide-angle X-ray diffraction pattern of 3(14/BF 4 ) at 80 C in the Col h phase. S20
3.4. POM, DSC, XRD, and Elemental Analysis Data on Compounds 4(n/BF 4 ) P BF4 4(10/BF 4 ) Elemental analysis calcd (%) for C 40 H 76 BF 4 O 3 P: C, 66.47; H, 10.60. Found: C, 66.39; H, 10.80. Figure S24. Polarizing optical microscopic image of 4(10/BF 4 ) in the Col h phase at 150 C. Figure S25. DSC thermograms of 4(10/BF 4 ). Figure S26. Wide-angle X-ray diffraction pattern of 4(10/BF 4 ) in the Col h phase at 80 C. S21
C 12 H 25 O C 12 H 25 O C 12 H 25 O P BF4 4(12/BF 4 ) Elemental analysis calcd (%) for C 46 H 88 BF 4 O 3 P: C, 68.47; H, 10.99. Found: C, 68.26; H, 11.20. Figure S27. Polarizing optical microscopic image of 4(12/BF 4 ) in the Col h phase at 170 C. Figure S28. DSC thermograms of 4(12/BF 4 ). Figure S29. Wide-angle X-ray diffraction pattern of 4(12/BF 4 ) in the Col h phase at 80 C. S22
C 14 H 29 O C 14 H 29 O C 14 H 29 O P BF4 4(14/BF 4 ) Elemental analysis calcd (%) for C 52 H 100 BF 4 O 3 P: C, 70.09; H, 11.31. Found: C, 69.98; H, 11.44. Figure S30. Polarizing optical microscopic image of 4(14/BF 4 ) in the Col h phase at 140 C. Figure S31. DSC thermograms of 4(14/BF 4 ). Figure S32. Wide-angle X-ray diffraction pattern of 4(14/BF 4 ) in the Col h phase at 80 C. S23
3.5. POM, DSC, XRD, and Elemental Analysis Data on Compounds 5(n/BF 4 ) P BF 4 5(10/BF 4 ) Elemental analysis calcd (%) for C 43 H 82 BF 4 O 3 P: C, 67.52; H, 10.81. Found: C, 67.42; H, 11.05. Figure S33. Polarizing optical microscopic image of 5(10/BF 4 ) in the Cub bi phase at 20 C. Figure S34. DSC thermograms of 5(10/BF 4 ). Figure S35. Wide-angle X-ray diffraction pattern of 5(10/BF 4 ) at 35 C in the Cub bi phase. S24
C 12 H 25 O C 12 H 25 O C 12 H 25 O 5(12/BF 4 ) P BF 4 Elemental analysis calcd (%) for C 49 H 94 BF 4 O 3 P: C, 69.32; H, 11.16. Found: C, 69.12; H, 11.44. Figure S36. Polarizing optical microscopic image of 5(12/BF 4 ) in the Col h phase at 80 C. Figure S37. DSC thermograms of 5(12/BF 4 ). Figure S38. Wide-angle X-ray diffraction pattern of 5(12/BF 4 ) in the Col h phase at 80 C. S25
C 14 H 29 O C 14 H 29 O C 14 H 29 O P BF 4 5(14/BF 4 ) Elemental analysis calcd (%) for C 55 H 106 BF 4 O 3 P: C, 70.79; H, 11.45. Found: C, 70.66; H, 11.70. Figure S39. Polarizing optical microscopic image of 5(14/BF 4 ) in the Col h phase at 120 C. Figure S40. DSC thermograms of 5(14/BF 4 ). Figure S41. Wide-angle X-ray diffraction pattern of 5(14/BF 4 ) in the Col h phase at 80 C. S26
3.6. POM, DSC, XRD, and Elemental Analysis Data on Compounds 6(n/BF 4 ) 6(10/BF 4 ) P BF 4 Elemental analysis calcd (%) for C 46 H 88 BF 4 O 3 P: C, 68.47; H, 10.99. Found: C, 68.42; H, 11.14. Figure S42. Polarizing optical microscopic image of 6(10/BF 4 ) in the Col h phase at 60 C. Figure S43. DSC thermograms of 6(10/BF 4 ). Figure S44. Wide-angle X-ray diffraction pattern of 6(10/BF 4 ) in the Col h phase at 60 C. S27
C 12 H 25 O C 12 H 25 O C 12 H 25 O P BF 4 6(12/BF 4 ) Elemental analysis calcd (%) for C 52 H 100 BF 4 O 3 P: C, 70.09; H, 11.31. Found: C, 70.13; H, 11.36. Figure S45. Polarizing optical microscopic image of 6(12/BF 4 ) in the Col h phase at 85 C. Figure S46. DSC thermograms of 6(12/BF 4 ). Figure S47. Wide-angle X-ray diffraction pattern of 6(12/BF 4 ) in the Col h phase at 80 C. S28
C 14 H 29 O C 14 H 29 O C 14 H 29 O P BF 4 6(14/BF 4 ) Elemental analysis calcd (%) for C 58 H 112 BF 4 O 3 P: C, 71.43; H, 11.57. Found: C, 71.40; H, 11.84. Figure S48. Polarizing optical microscopic image of 6(14/BF 4 ) in the Col h phase at 90 C. Figure S49. DSC thermograms of 6(14/BF 4 ). Figure S50. Wide-angle X-ray diffraction pattern of 6(14/BF 4 ) in the Col h phase at 80 C. S29
3.7. POM, DSC, XRD, and Elemental Analysis Data on Compounds 2(n/ PF 6 ) N PF 6 2(10/PF 6 ) Elemental analysis calcd (%) for C 43 H 82 F 6 NO 3 P: C, 64.07; H, 10.25; N, 1.74. Found: C, 64.18; H, 10.30; N, 1.95. Figure S51. Polarizing optical microscopic image of 2(10/PF 6 ) in the Cub bi phase at 25 C. Figure S52. DSC thermograms of 2(10/PF 6 ). S30
C 12 H 25 O C 12 H 25 O C 12 H 25 O 2(12/PF 6 ) N PF 6 Elemental analysis calcd (%) for C 49 H 94 F 6 NO 3 P: C, 66.11; H, 10.64; N, 1.57. Found: C, 65.96; H, 10.61; N, 1.69. Figure S53. Polarizing optical microscopic image of 2(12/PF 6 ) in the Cub bi phase at 50 C. Figure S54. DSC thermograms of 2(12/PF 6 ). Figure S55. Small-angle X-ray scattering pattern of 2(12/PF 6 ) in the Cub bi phase at 50 C. S31
C 14 H 29 O C 14 H 29 O C 14 H 29 O 2(14/PF 6 ) N PF 6 Elemental analysis calcd (%) for C 55 H 106 F 6 NO 3 P C, 67.79; H, 10.96; N, 1.44. Found: C, 67.76; H, 10.94; N, 1.61. Figure S56. Polarizing optical microscopic image of 2(14/PF 6 ) in the Col h phase at 110 C. Figure S57. DSC thermograms of 2(14/PF 6 ). Figure S58. Small-angle X-ray scattering pattern of 2(14/PF 6 ) in the Col h phase at 100 C. S32
3.8. POM, DSC, XRD, and Elemental Analysis Data on Compounds 2(n/CF 3 SO 3 ) N CF 3 SO 3 2(10/CF 3 SO 3 ) Elemental analysis calcd (%) for C 44 H 82 F 3 NO 6 S: C, 65.23; H, 10.20; N, 1.73. Found: C, 64.51; H, 10.10; N, 1.86. Figure S59. DSC thermograms of 2(10/CF 3 SO 3 ). C 12 H 25 O C 12 H 25 O C 12 H 25 O N CF 3 SO 3 2(12/CF 3 SO 3 ) Elemental analysis calcd (%) for C 50 H 94 F 3 NO 6 S: C, 67.15; H, 10.59; N, 1.57. Found: C, 66.97; H, 10.54; N, 1.69. Figure S60. DSC thermograms of 2(12/CF 3 SO 3 ). C 14 H 29 O C 14 H 29 O C 14 H 29 O N CF 3 SO 3 2(14/CF 3 SO 3 ) Elemental analysis calcd (%) for C 56 H 106 F 3 NO 6 S: C, 68.74; H, 10.92; N, 1.43. Found: C, 68.73; H, 10.97; N, 1.63. Figure S61. DSC thermograms of 2(14/CF 3 SO 3 ). S33
3.9. POM Results on Mixture of Compounds 5(10/BF 4 ) and LiBF 4 P BF 4 + LiBF 4 5(10/BF 4 ) Figure S62. Polarizing optical microscopic images of the mixture of 5(10/BF 4 )/LiBF 4 with a 4:1 molar ratio: (a) in the Col h phase at 105 C and (b) in the Cub bi phase at 30 C. S34
4. Synchrotron XRD Data used in the Construction of Electron Density Maps 2(10/BF 4 ) N BF 4 Figure S63. Powder diffraction pattern of 2(10/BF 4 ). Figure S64. Reconstructed electron density map of 2(10/BF 4 ) in the Cub bi phase at 20 C. Table S1. Experimental and calculated d-spacings of the observed SAXS reflections of the cubic phase in compound 2(10/BF 4 ) at 20 ºC. All intensities values are Lorentz corrected with correction for multiplicity. (hkl) d obs. spacing (Å) d cal. spacing (Å) intensity phase (211) 32.8 32.8 100.0 π (220) 28.5 28.4 29.0 π (321) 21.5 21.5 0.9 0 (400) 20.1 20.1 3.1 0 (420) 18.0 18.0 2.4 0 (332) 17.2 17.2 5.7 π (422) 16.5 16.4 2.1 π (431) 15.8 15.8 0.6 π a = b = c = 80.5 Å S35
5(10/BF 4 ) P BF 4 Figure S65. Powder diffraction pattern of 5(10/BF 4 ). Figure S66. Reconstructed electron density map of 5(10/BF 4 ) in the Cub bi phase at 20 C. Table S2. Experimental and calculated d-spacings of the observed SAXS reflections of the cubic phase in compound 5(10/BF 4 ) at 20 ºC. All intensities values are Lorentz corrected with correction for multiplicity. (hkl) d obs. spacing (Å) d cal. spacing (Å) intensity phase (211) 32.5 32.5 100.0 π (220) 28.2 28.2 24.6 π (321) 21.3 21.3 1.0 0 (400) 20.0 19.9 3.5 0 (420) 17.8 17.8 2.0 0 (332) 17.0 17.0 8.0 π (422) 16.3 16.3 2.6 π (431) 15.7 15.6 0.7 π a = b = c = 79.7 Å S36
2(10/PF 6 ) N PF 6 Figure S67. Powder diffraction pattern of 2(10/PF 6 ). Figure S68. Reconstructed electron density map of 2(10/PF 6 ) in the Cub bi phase at 20 C. Table 3. Experimental and calculated d-spacings of the observed SAXS reflections of the cubic phase in compound 2(10/PF 6 ) at 20 ºC. All intensities values are Lorentz corrected with correction for multiplicity. (hkl) d obs. spacing (Å) d cal. spacing (Å) intensity phase (211) 33.0 33.0 100.0 π (220) 28.6 28.5 27.8 π (321) 21.6 21.6 0.5 0 (400) 20.2 20.2 1.5 0 (420) 18.0 18.1 0.9 0 (332) 17.2 17.2 2.3 π (422) 16.5 16.5 0.9 π (431) 15.9 15.8 0.2 π a = b = c = 80.7 Å S37
5. Construction of Differential Electron Density Maps Samples 2(10/BF 4 ) and 2(10/PF 6 ) have the same cation (N + ) but different anions. The two samples have isomorphous structures, i.e. they both display the bicontinous cubic phase with very similar unit cell parameters: 8.05 nm for 2(10/BF 4 ) and 8.07 nm for 2(10/PF 6 ) (both values measured at 20 C). It is expected that the difference of the two structures come from the anions, while everything else remain essentially the same. The main difference between the two anion groups as seen by X-rays is that PF 6 has a higher electron density than BF 4. Consequently, if we subtract the electron density map of 2(10/BF 4 ) from that of 2(10/PF 6 ), the resulting difference map will enable us to locate the positions of the anions in the unit cell. A similar procedure has been applied previously in locating alkali metal cations in a micellar cubic phase. Before the difference between the two electron density maps can be calculated, the maps must be scaled to the same norm, since in normal SAXS experiment the diffraction intensities are collected in relative, not absolute terms (without corrections e.g. for beam intensity, sample volume, absorption etc). The common electron density scale can however be established by examining the volume fraction vs electron density histograms of the two reconstructed electron density maps, as shown in Figure S69. As the difference in the two maps should occur in the high electron density regions, we can scale the two histograms (original shown in Figure S69a) so that the low density regions match exactly, as shown in Figure S69b. The scaling factor can then be used to calculate the difference map between the two samples. (a) (b) Figure S69. Histrograms of the reconstructed electron density maps of 2(10/BF 4 ) and 2(10/PF 6 ). (a) Before scaling, (b) after scaling. The reconstructed map of 2(10/PF 6 ) and the difference map of 2(10/PF 6 ) minus 2(10/BF 4 ) are shown in Figure S70. Figure S70b clearly shows that the difference between the two maps, hence the location of the PF - 6 anions, is in the core of the bicontinuous networks. The high electron density regions in Figure S70b (red) are enclosed by the yellow isoelectron surface and occupy only 5% of the total volume. The remaining volume of the difference map surrounding the network core has a nearly flat near-zero differential electron density where the densities of 2(10/PF 6 ) and 2(10/BF 4 ) S38
cancel (blue). That the majority of the electron density in the difference map is nearly zero is shown most clearly in its histogram (Figure S71) where a sharp peak is seen at the low density end. For comparison, the original reconstructed map for 2(10/PF 6 ) is shown in Figure S70a, where an isoelectron surface encloses 5% of the total volume is also drawn. Here, however, the density of the remaining volume is far from flat, with minimum density located at the minimal surface (gyroid G-surface), shown in blue in the three 2D maps in the (100), (010) and (001) planes lining the walls of the diagram. High (a) (b) Low Figure S70. (a) Reconstructed electron density map of 2(10/PF 6 ), using the color palette on the right. (b) Difference map between 2(10/PF 6 ) and 2(10/BF 4 ). In both (a) and (b) the isoelectron surface encloses 5% of the total volume. 2D Electron density map in the (100), (010) and (001) plane of the unit cell are also shown by the side of the unit cell (slightly shifted to allow features to be seen behind the isoelectron surfaces). Figure S71. Histogram of the difference electron density map between 2(10/PF 6 ) and 2(10/BF 4 ). The narrow peak on the left marks zero difference. S39