Configuration Effects of H-Bonded Sites and Rigid Core Lengths on H-Bonded Banana-Shaped Liquid Crystalline
2.5. Electronic Supplementary Information 1. Synthesis
The synthetic procedures of all H-donors and H-accepters were proceeded according to scheme S2.1.
were prepared by following the literature procedures.13 A12: Yield: 92%, 1H NMR (300 MHz, DMSO-d6): δ 12.59 (s, 1H, COOH), 7.85 (d, J = 8.7 Hz, 2H, Ar-H), 6.98 (d, J = 8.7 Hz, 2H, Ar-H), 4.01 (t, J = 6.3 Hz, 2H, OCH2), 1.74-1.66 (m, 2H, OCH2CH2), 1.34-1.16 (m, 18H, CH2), 0.84 (t, J = 6.3 Hz, 3H, CH3); EIMS: m/e 306;
C19H30O3 requires m/e 306.44; EA: Calcd for C19H30O3: C, 74.47; H, 9.87;. Found: C, 74.44; H, 9.52. A16: Yield: 95%, 1H NMR (300 MHz, DMSO-d6): δ 12.59 (s, 1H, COOH), 7.85 (d, J = 8.7 Hz, 2H, Ar-H), 6.98 (d, J = 8.7 Hz, 2H, Ar-H), 4.01 (t, J = 6.3 Hz, 2H, OCH2), 1.72-1.65 (m, 2H, OCH2CH2), 1.39-1.15 (m, 28H, CH2), 0.84 (t, J
= 6.0 Hz, 3H, CH3); EIMS: m/e 363; C23H38O3 requires m/e 362.55; EA: Calcd for C23H38O3: C, 75.41; H, 10.25;. Found: C, 75.72; H, 10.37.
2.5.1.2. Synthesis of compound I. A mixture of resorcinol (1 eq.), isonicotinoyl chloride hydrochloride (1.1 eq.) and triethylamine was dissolved in dry dichloromethane (DCM) under nitrogen for 8 h at room temperature. After work up, the solvent was extracted with water/DCM and organic liquid layer was dried over anhydrous magnesium sulphate. After removal of the solvent by evaporation under reduced pressure, the residue was purified by column chromatography and recrystallized from THF/hexane to give a white solid. I : Yield: 74%, 1H NMR (300 MHz, DMSO-d6): δ 8.88 (d, J = 6.0 Hz, 2H, Ar-H), 8.01 (d, J = 6.0 Hz, 2H, Ar-H), 7.60 (t, J = 7.8 Hz, 1H, Ar-H), 7.44 (s, 1H, Ar-H), 7.34 (d, J = 8.7 Hz, 2H, Ar-H);
EIMS: m/e 320; C18H12N2O4 requires m/e 320.30; EA: Calcd for C18H12N2O4: N, 8.75 C, 67.50; H,3.78;. Found: N, 8.54 C, 67.43; H, 3.74.
2.5.1.3. Synthesis of compound 8. Resorcinol (1 eq.), benzyl bromide (1 eq.), K2CO3 (1 eq.) and acetone were mixed and stirred for 15h at reflux temperature. After reaction, acetone was removed by evaporation under reduced pressure, and the residue was extracted with water/DCM and the organic liquid layer was dried over anhydrous magnesium sulphate. After removal of the solvent by evaporation under
reduced pressure, the crude product was purified by column chromatography to get a waxed solid. Yield: 49%, 1H NMR (300 MHz, CDCl3): δ 7.43-7.30 (m, 5H, Ar-H), 7.12 (t, J = 7.8 Hz, 1H, Ar-H), 6.56 (d, J = 7.8 Hz, 1H, Ar-H), 6.48 (s, 1H, Ar-H), 6.42 (d, J = 7.8 Hz, 1H, Ar-H), 5.02 (s, 1H, -OH), 4.95 (s, 2H, OCH2).
2.5.1.4. Synthesis of compound 1 (n = 12 and 16). Am, compound 7, N,N-dicyclohexylcarbodiimide (DCC) (1.2 eq) and a catalytic amount of 4-(N,N-dimethylamino) pyridine (DMAP) was dissolved in dry dichloromethane (DCM) under nitrogen for 15 h at room temperature. The precipitated dicyclohexylurea (DCU) was filtered off and washed with an excess of DCM (20 ml).
The filtrate was extracted with water/DCM and the organic liquid layer was dried over anhydrous magnesium sulphate. After removal of the solvent by evaporation under reduced pressure, the residue was recrystallized from ethanol to give a white solid. 1/12: Yield: 71%, 1H NMR (300 MHz, CDCl3): δ 8.20-8.15 (m, 4H, Ar-H), 7.51 (d, J = 8.7 Hz, 2H, Ar-H), 7.46-7.37 (m, 5H, Ar-H), 7.04 (d, J = 9.0 Hz, 2H, Ar-H), 6.95-6.82 (m, 3H, Ar-H), 5.07 (s, 2H, -OCH2-), 4.10 (t, J = 6.3 Hz, 2H, OCH2), 1.80 (m, 2H, OCH2CH2), 1.28 (m, 18H, CH2), 0.88 (s, 3H, -CH3). 1/16: Yield: 73%, 1H NMR (300 MHz, CDCl3): δ 8.18 (d, J = 9.0 Hz, 2H, Ar-H), 8.15 (d, J = 8.4 Hz, 2H, Ar-H), 7.52 (d, J = 8.4 Hz, 2H, Ar-H), 7.45-7.36 (m, 5H, Ar-H), 7.08 (d, J = 9.0 Hz, 2H, Ar-H), 5.40 (s, 2H, -OCH2-), 4.10 (t, J = 6.3 Hz, 2H, OCH2), 1.86-1.81 (m, 2H, OCH2CH2), 1.51-1.31 (m, 28H, CH2), 0.92 (t, J = 6.3 Hz, 3H, CH3).
2.5.1.5. Synthesis of compound Bm (m = 12 and 16). Compound 1 and Pd/C catalyst were stirred in THF under hydrogen at room temperature. The catalyst was removed by filtration through Celite and washed with THF. The solvent was removed by evaporation under reduced pressure and the crude product was recrystallized by THF/hexane to give a white solid. B12: Yield: 92%, 1H NMR (300 MHz, CDCl3): δ
7.31 (d, J = 8.4 Hz, 2H, Ar-H), 6.96 (d, J = 8.7 Hz, 2H, Ar-H), 4.07 (t, J = 6.6 Hz, 2H, OCH2), 1.78-1.68 (m, 2H, OCH2CH2), 1.38-1.26 (m, 18H, CH2), 0.85 (t, J = 6.6 Hz, 3H, CH3); EIMS: m/e 426; C26H34O3 requires m/e 426.55; EA: Calcd for C26H34O3: C, 73.21; H, 8.03;. Found: C, 73.21; H, 8.06. B16: Yield: 90%, 1H NMR (300 MHz, DMSO-d6): δ 13.02 (s, 1H, COOH), 8.06 (d, J = 8.7 Hz, 2H, Ar-H) 8.01 (d, J = 9.0 Hz, 2H, Ar-H) 7.38 (d, J = 8.7 Hz, 2H, Ar-H), 7.10 (d, J = 9.0 Hz, 2H, Ar-H), 4.07 (t, J = 6.3 Hz, 2H, OCH2), 1.75-1.70 (m, 2H, OCH2CH2), 1.41-1.22 (m, 28H, CH2), 0.83 (t, J
= 5.7 Hz, 3H, CH3); FABMS: m/e 484; C30H42O3 requires m/e 482.65; EA: Calcd for C30H42O3: C, 74.65; H, 8.77. Found: C, 74.71; H, 8.80.
2.5.1.6. Synthesis of compound 2 (n = 12 and 16). By following the similar esterification procedure of compound 1, compounds Bm (1 eq.) and compound 8 (1.2 eq.) were reacted to obtain a white solid. 2/12: Yield: 72% 1H NMR (300 MHz, DMSO-d6); δ 8.16 (d, J = 8.7 Hz, 2H, Ar-H), 8.08 (d, J = 8.7 Hz, 2H, Ar-H), 7.49 (d, J
= 8.7 Hz, 2H, Ar-H), 7.46-7.32 (m, 6H, Ar-H), 7.11 (d, J = 8.7 Hz, 2H, Ar-H), 7.01 (s, 1H, Ar-H), 6.96 (d, J = 8.1 Hz, 1H, Ar-H), 6.88 (d, J = 8.1 Hz, 1H, Ar-H), 5.11 (s, 2H, OCH2), 4.08 (t, J = 6.6 Hz, 2H, OCH2), 1.73 (t, J = 6.3 Hz, 2H, OCH2CH2), 1.41-1.23 (m, 18H, CH2), 0.92 (t, J = 6.6 Hz, 3H, CH3). 2/16: Yield: 79% 1H NMR (300 MHz, CDCl3); δ 8.25 (d, J = 8.7 Hz, 2H, Ar-H), 8.13 (d, J = 9.0 Hz, 2H, Ar-H), 7.42-7.29 (m, 8H, Ar-H), 6.94 (d, J = 9.0 Hz, 2H, Ar-H), 6.90-6.81 (m, 3H, Ar-H), 5.06 (s, 2H, OCH2), 4.04 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (t, J = 6.6 Hz, 2H, OCH2CH2), 1.45-1.24 (m, 28H, CH2), 0.86 (t, J = 6.3 Hz, 3H, CH3).
2.5.1.7. Synthesis of compound 3 (n = 12 and 16). By following the similar deprotection procedure of compounds Bm, compound 2 were reacted Pd/C catalyst to yield a white solid. 3/12: Yield: 95%, 1H NMR (300 MHz, DMSO-d6): δ 8.25 (d, J = 8.7 Hz, 2H, Ar-H), 8.14 (d, J = 9.0 Hz, 2H, Ar-H), 7.40 (d, J = 8.7 Hz, 2H, Ar-H), 7.22 (t, J = 8.1 Hz, 1H, Ar-H), 7.03 (d, J = 9.0 Hz, 2H, Ar-H), 6.71-6.66 (m, 3H,
Ar-H), 4.06 (t, J = 6.6 Hz, 2H, OCH2), 1.80 (m, 2H, OCH2CH2), 1.47-1.28 (m, 18H, CH2), 0.88 (t, J = 6.3 Hz, 3H, CH3). 3/16: Yield: 98%, 1H NMR (300 MHz, CDCl3): δ 8.24 (d, J = 8.7 Hz, 2H, Ar-H), 8.12 (d, J = 9.0 Hz, 2H, Ar-H), 7.34 (d, J = 8.7 Hz, 2H, Ar-H), 7.26 (t, J = 8.4 Hz, 1H, Ar-H), 6.96 (d, J = 9.0 Hz, 2H, Ar-H), 6.79-6.71 (m, 3H, Ar-H), 4.04 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (t, J = 6.6 Hz, 2H, OCH2CH2), 1.46-1.25 (m, 28H, CH2), 0.86 (t, J = 6.6 Hz, 3H, CH3). ;
2.5.1.8. Synthesis of compound IVn (n = 12 and 16). Compound 3 (1 eq.), isonicotinoyl chloride hydrochloride (1.1 eq.) and triethylamine were reacted according to the similar esterification procedure of compound I to get a white solid.
IV12 : Yield: 95%, 1H NMR (300 MHz, DMSO-d6): δ 8.89 (d, J = 4.2 Hz, 2H, Ar-H), 8.22 (d, J = 8.7 Hz, 2H, Ar-H), 8.08(d, J = 8.7 Hz, 2H, Ar-H), 8.01 (d, J = 4.2 Hz, 2H, Ar-H), 7.59 (t, J = 8.1 Hz, 1H, Ar-H), 7.51 (d, J = 9.0 Hz, 2H, Ar-H), 7.41 (s, 1H, Ar-H), 7.32 (br, 2H, Ar-H), 7.10 (d, J = 9.0 Hz, 2H, Ar-H); 4.07 (t, J = 6.3 Hz, 2H, OCH2), 1.74 (br, 2H, OCH2CH2), 1.23 (br, 18H, CH2), 0.84 (t, J = 6.3 Hz, 3H, CH3);
FABMS: m/e 624; C38H41NO7 requires m/e 623.73; EA: Calcd for C38H41NO7: N, 2.25 C, 73.17; H, 6.63;. Found: N, 2.44 C, 73.25; H, 6.75. IV16 : Yield: 89%, 1H NMR (300 MHz, DMSO-d6): δ 8.81 (d, J = 6.0 Hz, 2H, Ar-H), 8.25 (d, J = 9.0 Hz, 2H, Ar-H), 8.10 (d, J = 9.0 Hz, 2H, Ar-H), 7.98 (d, J = 6.0 Hz, 2H, Ar-H), 7.49 (t, J = 8.1 Hz, 1H, Ar-H), 7.38 (d, J = 9.0 Hz, 2H, Ar-H), 7.27 (s, 1H, Ar-H), 7.22-7.17 (m, 2H, Ar-H), 7.01 (d, J = 9.0 Hz, 2H, Ar-H); 4.03 (t, J = 6.6 Hz, 2H, OCH2), 1.79-1.75 (m, 2H, OCH2CH2), 1.45-1.24 (m, 28H, CH2), 0.84 (t, J = 6.6 Hz, 3H, CH3); FABMS:
m/e 681; C38H41NO7 requires m/e 679.84; EA: Calcd for C42H49NO7: N, 2.06 C, 74.20;
H, 7.26. Found: N, 2.17 C, 74.24; H, 7.18.
2.5.1.9. Synthesis of compound 4 (n = 12 and 16). Compounds Bm (1 eq.) and compound 7 (1.2 eq.) were reacted by following the esterification procedure of
δ 8.27 (d, J = 8.7 Hz, 2H, Ar-H), 8.17 (d, J = 9.0 Hz, 2H, Ar-H), 8.15 (d, J = 9.0 Hz, 2H, Ar-H), 7.47-7.35 (m, 7H, Ar-H), 7.31 (d, J = 9.0 Hz, 2H, Ar-H), 7.00 (d, J = 9.0 Hz, 2H, Ar-H), 5.38 (s, 2H, -OCH2-), 4.05 (t, J = 6.0 Hz, 2H, OCH2), 1.87-1.80 (m, 2H, OCH2CH2), 1.48-1.27 (m, 18H, CH2), 0.88 (t, J = 5.4 Hz, 3H, -CH3).; 4/16: Yield:
73%, 1H NMR (300 MHz, CDCl3) δ 8.21 (d, J = 8.7 Hz, 2H, Ar-H), 8.13 (d, J = 8.7 Hz, 2H, Ar-H), 8.10 (d, J = 9.0 Hz, 2H, Ar-H), 7.42-7.30 (m, 7H, Ar-H), 7.24 (d, J = 8.7 Hz, 2H, Ar-H), 6.95 (d, J = 9.0 Hz, 2H, Ar-H), 5.43 (s, 2H, -OCH2-), 4.03 (t, J = 6.0 Hz, 2H, OCH2), 1.81-1.72 (m, 2H, OCH2CH2), 1.44-1.23 (m, 28H, CH2), 0.86 (s, 3H, -CH3).
2.5.1.10. Synthesis of compound Cm (m = 12 and 16). By following the similar deprotection procedure of compounds Bm, compound 4 were reacted Pd/C catalyst to yield a white solid. C12: Yield: 94%, 1H NMR (300 MHz, DMSO-d6) δ 8.32 (d, J = 8.7 Hz, 2H, Ar-H), 8.18 (d, J = 8.7 Hz, 2H, Ar-H), 8.14 (d, J = 8.7 Hz, 2H, Ar-H), 7.47 (d, J = 8.7 Hz, 2H, Ar-H), 7.41 (d, J = 8.7 Hz, 2H, Ar-H), 7.10 (d, J = 8.7 Hz, 2H, Ar-H), 4.11 (t, J = 6.3 Hz, 2H, OCH2), 1.82 (m, 2H, OCH2CH2), 1.46-1.25 (m, 18H, CH2), 0.92 (t, J = 4.8 Hz, 3H, CH3).; FBMS: m/e 547; C33H38O7 requires m/e 546.65; EA: Calcd for C33H38O7: C, 72.51; H, 7.1. Found: C, 72.11; H, 6.99. C16:
Yield: 98%, 1H NMR (300 MHz, DMSO-d6) δ 8.25 (d, J = 8.7 Hz, 2H, Ar-H), 8.10 (d, J = 8.1 Hz, 2H, Ar-H), 8.07 (d, J = 8.4 Hz, 2H, Ar-H), 7.39 (d, J = 8.7 Hz, 2H, Ar-H),
7.32 (d, J = 8.1 Hz, 2H, Ar-H), 7.01 (d, J = 8.4 Hz, 2H, Ar-H), 4.03 (t, J = 6.3 Hz, 2H, OCH2), 1.76 (br, 2H, OCH2CH2), 1.43-1.24 (m, 28H, CH2), 0.84 (t, J = 4.8 Hz, 3H, CH3).; FBMS: m/e 603; C37H46O7 requires m/e 602.76; EA: Calcd for C37H46O7: C, 73.73; H, 7.69. Found: C, 73.86; H, 7.72.
2.5.1.11. Synthesis of compound 5 (n = 12 and 16). Compounds Cm (1 eq.) and compound 8 (1.2 eq.) were reacted by following the esterification procedure of compound 1 to acquire a white solid. 5/12: Yield: 73%, 1H NMR (300 MHz, DMSO)
8.25 (d, J = 9.0 Hz, 2H, Ar-H), 8.23 (d, J = 8.7 Hz, 2H, Ar-H), 8.10 (d, J = 8.4 Hz, 2H, Ar-H), 7.56 (d, J = 9.0 Hz, 2H, Ar-H), 7.53 (d, J = 8.7 Hz, 2H, Ar-H), 7.47 (s, 1H, Ar-H), 7.45-7.33 (m, 5H, Ar-H), 7.12 (d, J = 8.4 Hz, 2H, Ar-H), 7.03 (t, J = 8.1Hz, 1H, Ar-H), 6.98 (d, J = 8.1Hz, 1H, Ar-H), 6.90 (d, J = 8.1 Hz, 1H, Ar-H), 5.12 (s, 2H, OCH2), 4.09 (t, J = 6.3 Hz, 3H, OCH2), 1.74 (br, 2H, OCH2CH2), 1.40-1.23 (m, 18H, CH2), 0.84 (t, J = 5.7 Hz, 3H, CH3). 5/16: Yield: 81%, 1H NMR (300 MHz, DMSO) 8.26 (d, J = 9.6 Hz, 2H, Ar-H), 8.23 (d, J = 8.7 Hz, 2H, Ar-H), 8.10 (d, J = 8.7 Hz, 2H, Ar-H), 7.56 (d, J = 9.6 Hz, 2H, Ar-H), 7.53 (d, J = 8.7 Hz, 2H, Ar-H), 7.47 (s, 1H, Ar-H), 7.45-7.33 (m, 5H, Ar-H), 7.13 (d, J = 8.7 Hz, 2H, Ar-H), 7.02 (t, J = 7.5Hz, 1H, Ar-H), 6.97 (d, J = 7.5Hz, 1H, Ar-H), 6.89 (d, J = 7.5 Hz, 1H, Ar-H), 5.13 (s, 2H, OCH2), 4.10 (t, J = 6.3 Hz, 3H, OCH2), 1.73 (br, 2H, OCH2CH2), 1.43-1.23 (m, 28H, CH2), 0.83 (t, J = 5.7 Hz, 3H, CH3).
2.5.1.12. Synthesis of compound 6 (n = 12 and 16). By following the similar deprotection procedure of compounds Bm, compound 5 were reacted Pd/C catalyst to yield a white solid. 6/12: Yield: 95%, 1H NMR (300 MHz, DMSO-d6); δ 8.26 (d, J = 8.7 Hz, 4H, Ar-H), 8.14 (d, J = 8.1 Hz, 2H, Ar-H), 7.45 (d, J = 8.4 Hz, 4H, Ar-H), 7.25 (t, J = 8.1 Hz, 1H, Ar-H), 7.07 (d, J = 8.4 Hz, 2H, Ar-H), 6.71-6.69 (m, 3H, Ar-H), 4.10 (t, J = 6.3 Hz, 2H, OCH2), 1.82 (t, J = 6.6 Hz, 2H, OCH2CH2), 1.43-1.22 (m, 18H, CH2), 0.86 (t, J = 6.6 Hz, 3H, CH3). 6/16: Yield: 91%, 1H NMR (300 MHz, DMSO-d6) δ 8.25 (d, J = 9.0 Hz, 4H, Ar-H), 8.11 (d, J = 8.4 Hz, 2H, Ar-H), 7.41 (d, J
= 8.4 Hz, 4H, Ar-H), 7.19 (t, J = 8.4 Hz, 1H, Ar-H), 7.02 (d, J = 8.4 Hz, 2H, Ar-H), 6.69-6.64 (m, 3H, Ar-H), 4.04 (t, J = 6.6 Hz, 2H, OCH2), 1.78 (t, J = 6.9 Hz, 2H, OCH2CH2), 1.45-1.23 (m, 28H, CH2), 0.85 (t, J = 6.6 Hz, 3H, CH3).
2.5.1.13. Synthesis of compound Vn (n = 12 and 16). Compound 6 (1 eq.), isonicotinoyl chloride hydrochloride (1.1 eq.) and triethylamine were reacted
V12: Yield: 95%, 1H NMR (300 MHz, DMSO-d6) δ 8.89 (d, J = 5.4 Hz, 2H, Ar-H), 8.25 (d, J = 8.7 Hz, 4H, Ar-H), 8.10 (d, J = 8.7 Hz, 2H, Ar-H), 8.02 (d, J = 5.4 Hz, 2H, Ar-H), 7.27-7.52 (m, 5H, Ar-H), 7.42 (s, 1H, Ar-H), 7.34 (d, J = 8.7 Hz, 2H, Ar-H), 7.12 (d, J = 8.7 Hz, 2H, Ar-H). 4.09 (t, J = 6.6 Hz, 2H, OCH2), 1.74 (t, J = 6.3 Hz, 2H, OCH2CH2), 1.42-1.24 (m, 18H, CH2), 0.84 (t, J = 6.6 Hz, 3H, CH3).; EIMS: m/e 744;
C45H45NO9 requires m/e 743.84; EA: Calcd for C45H45NO9: N, 1.88; C, 72.66; H, 6.10.
Found: N, 1.98; C, 72.69; H, 5.98. V16: Yield: 91%, 1H NMR (300 MHz, DMSO-d6) δ 8.81 (d, J = 4.8 Hz, 2H, Ar-H), 8.27 (d, J = 9.0 Hz, 4H, Ar-H), 8.11 (d, J = 9.0 Hz, 2H, Ar-H), 8.02 (d, J = 4.8 Hz, 2H, Ar-H), 7.50 (t, J = 8.1 Hz, 1H, Ar-H), 7.44 (d, J = 8.7 Hz, 2H, Ar-H), 7.42 (d, J = 8.4 Hz, 2H, Ar-H), 7.27 (s, 1H, Ar-H), 7.23-7.18 (m, 2H, Ar-H), 7.02 (d, J = 9.0 Hz, 2H, Ar-H), 4.04 (t, J = 6.3 Hz, 2H, OCH2), 1.77 (t, J = 6.6 Hz, 2H, OCH2CH2), 1.45-1.28 (m, 28H, CH2), 0.85 (t, J = 5.4 Hz, 3H, CH3).;
EIMS: m/e 801; C49H53NO9 requires m/e 799.95; EA: Calcd for C49H53NO9: N, 1.75;
C, 73.57; H, 6.68;. Found: N, 1.94; C, 73.69; H, 6.49.
2.5.1.14. Synthesis of compound 10. Methyl 4-hydroxybenzoate (1eq.), benzyl bromide (1.1eq.), and K2CO3 (1.5eq.) were reacted in acetone at reflux temperature for 10h. After removing acetone at reduced pressure, the precipitate was produced immediately by adding water. The crude product was recrystallized from acetone/hexane to give a white solid. 10: Yield: 97%, 1H NMR (300 MHz, CDCl3) δ 7.03 (d, J = 9.0 Hz, 2H, Ar-H), 6.63-6.50 (m, 5H, Ar-H), 6.35 (d, J = 9.0 Hz, Ar-H), 4.38 (s, 2H, OCH2), 2.49 (s, 3H, OCH3).
2.5.1.15. Synthesis of compound 11. Compound 10 (1eq.) and KOH (4eq.) were reacted in ethanol at reflux temperature for 10h. Water was added to produce the precipitate, and the crude product was recrystallized from THF/hexane to give a white solid. 11: Yield: 98%, 1H NMR (300 MHz, DMSO) δ 7.87 (d, J = 9.0 Hz, 2H, Ar-H), 7.46-7.33 (m, 5H, Ar-H), 7.07 (d, J = 9.0 Hz. 2H, Ar-H), 5.17 (s, 2H, OCH2).
2.5.1.16. Synthesis of compound 12. Compound 11 (2.2 eq.) and compound 9 (1 eq.) were reacted by following the esterification procedure of compound 1 to acquire a white solid. 12: Yield: 75%, 1H NMR (300 MHz, CDCl3) δ 8.15 (d, J = 9.0 Hz. 4H, Ar-H), 7.48-7.33 (m, 11H, Ar-H), 7.13 (d, J = 9.0 Hz. 2H, Ar-H), 7.12 (s, 1H, Ar-H), 7.05 (d, J = 9.0 Hz. 4H, Ar-H), 5.16 (s, 4H, OCH2).
2.5.1.17. Synthesis of compound 13. By following the similar deprotection procedure of compounds Bm, compound 12 were reacted Pd/C catalyst to yield a white solid. 13: Yield: 95%, 1H NMR (300 MHz, CDCl3) δ 7.98 (d, J = 9.0 Hz. 4H, Ar-H), 7.51 (t, J = 7.5 Hz. 1H, Ar-H), 7.06 (d, J = 7.5 Hz. 2H, Ar-H), 7.03 (s, 1H, Ar-H), 6.92 (d, J = 9.0 Hz. 4H, Ar-H).
2.5.1.18. Synthesis of compound II. Compound 13 (1 eq.), isonicotinoyl chloride hydrochloride (2.4 eq.) and triethylamine were reacted according to the similar esterification procedure of compound I to get a white solid. II: Yield: 84%, 1H NMR (300 MHz, DMSO-d6) δ 8.92 (d, J = 5.4 Hz, 4H, Ar-H), 8.38 (d, J = 8.4 Hz, 4H, Ar-H), 8.10 (d, J = 5.4 Hz, 4H, Ar-H), 7.60 (t, J = 7.8 Hz, 1H, Ar-H), 7.55 (d, J = 8.4 Hz, 4H, Ar-H), 7.34-7.28 (m, 3H, Ar-H).; FBMS: m/e 562; C32H20N2O8 requires m/e 560.51; EA: Calcd for C32H20N2O8: N, 5.00; C, 68.57; H, 3.60;. Found: N, 5.07; C, 68.43; H, 3.84.
2.5.1.19. Synthesis of compound IIIn. Compounds Bm (1 eq.) and compound 14 (1 eq.) were reacted by following the esterification procedure of compound 1 to acquire a white solid. III12: Yield: 86%, 1H NMR (300 MHz, DMSO-d6) δ 8.61 (s, 1H, Ar-H), 8.30 (d, J = 6.0 Hz, 1H, Ar-H), 8.25 (d, J = 8.7 Hz, 2H, Ar-H), 8.10 (d, J = 8.7 Hz, 2H, Ar-H), 7.85-7.82 (m, 1H, Ar-H), 7.57 (m. 1H, Ar-H), 7.53 (d, J = 8.7 Hz, 2H, Ar-H), 7.12 (d, J = 8.7 Hz, 2H, Ar-H), 4.09 (t, J = 6.3 Hz, 2H, OCH2), 1.73 (m, 2H, OCH2CH2), 1.49-1.24 (m, 18H, CH2), 0.84 (t, J = 6.3 Hz, 3H, CH3).; EIMS: m/e
7.41. Found: N, 2.81; C, 73.67; H, 7.35. III16: Yield: 82%, 1H NMR (300 MHz, DMSO-d6) δ 8.51 (s, 1H, Ar-H), 8.46 (d, J = 4.5 Hz, 1H, Ar-H), 8.26 (d, J = 8.7 Hz, 2H, Ar-H), 8.11 (d, J = 8.7 Hz, 2H, Ar-H), 7.63-7.62 (m, 1H, Ar-H), 7.42 (s. 1H, Ar-H), 7.39 (d, J = 8.7 Hz, 2H, Ar-H), 7.02 (d, J = 8.7 Hz, 2H, Ar-H), 4.03 (t, J = 6.3 Hz, 2H, OCH2), 1.77 (t, J = 6.6 Hz, 2H, OCH2CH2), 1.44-1.24 (m, 28H, CH2), 0.84 (t, J = 5.4 Hz, 3H, CH3).; EIMS: m/e 559; C35H45NO5 requires m/e 559; EA: Calcd for C35H45NO5: N, 2.50; C, 75.10; H, 8.10. Found: N, 2.85; C, 74.95; H, 8.11.
O
Scheme S2.1. Synthetic procedures of H-donors and H-acceptors Am, Bm, Cm, I, II, IIIn, IVn, and Vn (n and m = 12, 16). (i): DCC, DMAP, DCM; (ii): Pd/C, H2, THF; (iii): isonicotinoyl chloride hydrochloride, Et3N, DCM; (iv): benzyl bromide,
0
Figure S2.1. Phase diagram of (a) H-acceptors (Am, Bm, and Cm) and (b) H-donors (I, II, IIIn, IVn, and Vn).
0 100 200 300 400 500 600 0
100 200 300 400 500 600
Ps (nC/cm2 )
Applied Voltage (Vpp)
S12
V = 320 Vpp
Figure S2.2. Ps values vs. applied voltages for compound S12.
Figure S2.3. Low energy structures of S1 optimized at B3LYP/6-31G(d).
Conf 1 Conf 4
Conf 5
Conf 6 Conf 2
Conf 3 X
Y
Figure S2.4. Low energy structures of I-A1 optimized at B3LYP/6-31G(d).
Figure S2.5. Low energy structures of IV1-A1 optimized at B3LYP/6-31G(d).
Conf 2
Conf 3 Conf 1
Conf 4 X
Y
Conf 1
Conf 2
Conf 3
Conf 4 X
Figure S2.6. Low energy structures of III1-B1 optimized at B3LYP/6-31G(d).
Conf 2
Conf 3 Conf 1
Conf 4
Conf 5 Conf 6
Conf 7 Conf 8
Conf 9 X
Y
Table S2.1. Phase Transition Temperatures and Enthalpies of H-Donors (Am, Bm, and Cm) and H-Acceptors (I, II, IIIn, IVn, and Vn)
Compd. Phase transition temperature/oC [Enthalpy/kJ/g]
A12 I 135.5 [8.09] N 129.2 [6.3] SmC 86.5 [40.2] K A16 I 127.1 [25.8] SmC 83.7 [71.5] K
B12 I 203.9 [7.7] SmC 104.7 [46.2] K B16 I 198.6 [8.5] SmC 105.3 [40.3] K
C12 I 289a N 218.8 [2.9] SmC 139.5 [13.6] K
C16 I 283a N 220.3 [1.7] SmC 135.4 [15.9] K
I I 93.5 [104.8] K II I 141.4 [89.5] K III12 I 83.6 [99.4] K III16 I 81.0 [106.8] K
IV12 I 105.4 [2.5] N 85.3 [48.2] K IV16 I 100.5 [93.9] K
V12 I 148.1 [4.9] N 124.5 [64.4] K V16 I 147.4 [4.4] N 135.7 [66.6] K
I = isoptropic state; N = nematic phase; SmC = normal tilt smectic phase; K = crystalline state. a means the temperature data is observed in POM only. The phase transitions were measured by DSC at the 2nd cooling scan with a cooling rate of 5°Cmin-1.
Table S2.2. Sets of Low Energy Structures Calculated at B3LYP/6-31G(d) of the Bent-Core Structures of S1, I-A1, IV1-A1, and III1-B1
conform
a Bent angle (°) measured as the angle between the first, central and final benzene rings’ centers of the bent-core structures.