Supporting Information · 2018. 1. 31. · - 1 - Supporting Information Systematic exploitation of thermotropic bicontinuous cubic phase families from 1,2-bis(aryloyl)hydrazine-based

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Supporting Information

Systematic exploitation of thermotropic bicontinuous cubic phase families from

1,2-bis(aryloyl)hydrazine-based molecules

Shoichi Kutsumizu,* Yutaro Yamada, Tadashi Sugimoto, Nina Yamada,

Taro Udagawa, and Yohei Miwa

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan

Table of contents 1. Synthesis and characterization 2. Detailed synthesis procedures and characterization data 3. DSC data 4. XRD data 5. POM 6. Computational detail and cartesian coordinates of the optimized structures 7. IR data 8. References

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2018

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1. Synthesis and characterization 1.1. Synthesis

Scheme S1 shows the preparation routes for symmetric and unsymmetric

compounds examined in the first and second strategies. For the symmetric compounds, starting from the carboxylic acids having long alkyl tails, they were converted into the acid chlorides and then, the two molecules were coupled with a hydrazine to obtain the

Scheme S1. (i) SOCl2, reflux; (ii) N2H4H2O, r.t.; (iii) DIPEA, 80-100 C; (iv) PdCl2(PPh3)2, PPh3, CuI, Et3N, reflux; (v) DIBAL, NaOH; (vi) activated MnO2, reflux, 80 C; (vii) N2H4H2O, r.t..

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final symmetric compounds. In the case of the PEB series, a slight different route was employed; and initially the bis(benzoyl)hydrazine cores were prepared and then, the cores were extended by attaching p-alkoxyphenylacetylene to both terminals. To examine the role of hydrogen bonding interaction acting with the molecular core in the phase behavior, the bis(phenylbenzylidene)hydrazine core was selected. Starting from the carboxylate ester having long alkyl tails, the phenyl benzyl alcohol was prepared and then, changed to the corresponding aldehyde, and finally, two aldehydes were coupled with a hydrazine to obtain the final symmetric compound having n = 22 tails PBID-22 (9a). For the unsymmetric compounds, the acid chlorides and acid hydrazides were initially prepared to incorporate different aromatic cores with different sizes in them, and they were combined. 1.2. Characterization

All solvents and reagents were obtained from commercial sources and used without further purification unless noted. The purity and characterization of all intermediary compounds and the final compounds were checked by a combination of thin-layer chromatography (TLC: on silica gel coated glass plates (Merck) with fluorescent indicator), NMR spectroscopy, and elemental analysis. 1H NMR (400 or 600 MHz) spectra were recorded on a JEOL ECA600 or a JEOL ECS400 spectrometer, and CDCl3, pyridine-d5, tolune-d8, THD-d8, DMSO-d6, and DMF-d7 were as solvents and tetramethysilane (TMS) was used as internal standard ( = 0.00). Chemical shifts are reported as in parts per million downfield from TMS. Elemental analyses were carried out at Laboratory of Organic Elemental Microanalysis, Kyoto University, and performed using a J-Science Labo micro corder JM10 at Division Instrumental Analysis, Life Science Research Center, Gifu University. Phase transitions were determined by using a Seiko Denshi DSC-200 interfaced to a TA data station (SSC 5000 system) and a SII Nanotechnologies DSC7020. The measurements were performed under a dry N2 flow of c. 40 mL min-1 and the scanning rate was 5 K min-1. The texture of each mesophase was observed usually under crossed polarizers using polarizing optical microscopes (POM; a Nikon Optiphot-pol XTP-11 and an Olympus BX53P) equipped with a Mettler FP82HT hotstage and a Mettler FP90 controller. The scanning rate was 5 or 1 K min-1. For the observation of a conglomerate of chiral domains, the sample was heated to an objective temperature from room temperature at 10 K min-1 and the sample thickness was 44 m using a PET film spacer. The brightness of the two kinds of domains were inverted when the position of the analyzer was changed from +10 to 10 out of the precise 90 position with respect to

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the polarizer. X-ray diffraction (XRD) patterns at elevated temperatures were obtained for powder samples using a Rigaku NANO-Viewer IP system. CuK radiation was used at 45 kV and 60 mA. The scattered X-rays were recorded on a two-dimensional imaging plate (IP). The intensities were radially integrated and averaged, and redistributed when converting the pixel number into the corresponding scattering vector q (q = (4/)sin, with being the X-rays wavelength (= 0.15418 nm) and 2 the scattering angle) to produce a circularly averaged pattern. In some cases, to confirm the phase behaviors in detail, time-resolved XRD measurements were performed using synchrotron radiation at the Photon Factory (PF) in the High-Energy Accelerator Research Organization (KEK). The sizes of the molecular cores were evaluated on the basis of M06/6-31G* density functional theory. The detailed computational procedures are given in section 6.

FT-IR spectra were recorded with a Jasco FT-IR-460 Plus / IRT-30 spectrometer equipped with a Mettler FP82HT hotstage and a Mettler FP90 controller at Division Instrumental Analysis, Life Science Research Center, Gifu University. The samples were sandwiched between two KBr plates (551 mm3) and placed on the hotstage. The measurements were performed on the transmittance mode with 100 scans at 4 cm-1 optical resolution. The sample room was purged with N2 gas. 2. Detailed synthesis procedures and characterization data 1a. 1,2-Bis(4-n-dodecyloxynaphthoyl)hydrazine (N-12) First step (preparation of ethyl 6-hydroxy-2-naphthoate):S1 6-hydroxy-2-naphthoic acid (10.07 g, 53.5 mmol) was dissolved in ethanol (200 mL), to which concentrated H2SO4 (5.00 g, 51.0 mmol) was added dropwise. The mixture was then refluxed at 100 C for 24 h. After cooled, the solvent was removed with a rotary evaporator. The product in the organic layer was extracted with CHCl3 (500 mL) and 5 % K2CO3 aqueous solution (100 mL), and washed with water thoroughly until neutral. After that, the solvent was dried with MgSO4, removed under a reduced pressure to give a yellowish white crystalline solid, identified by 1H NMR. Yield 11.42 g (52.9 mmol), 99 %. 1H NMR (400 MHz, CDCl3, r.t.): δ 8.54 (s, 1H, Ar-H), 8.02 (dd, J1 = 8.5 Hz, J2 = 1.7 Hz, 1H, Ar−H), 7.87 (d, J = 8.3 Hz, 1H, Ar−H), 7.70 (d, J = 8.8 Hz, 1H, Ar−H), 7.19 (s, 1H, Ar−H), 7.17 (dd, J1 = 9.2 Hz, J2 = 2.4 Hz,d, 1H, Ar−H), 5.49 (s, 1H, OH), 4.44 (q, J = 7.1 Hz, 2H, COOCH2), 1.44 (t, J = 7.3 Hz, 3H, COOCH2CH3). Second step (preparation of 6-n-dodecyloxy-2-naphthoic acid):S1 Ethyl 6-hydroxy-2-naphthoate (5.36 g, 24.7 mmol), 1-bromo-n-dodecane (7.46 g, 29.9 mmol), and K2CO3

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(6.31 g, 45.7 mmol) were dissolved in acetone (200 mL), and stirred at 60 C for 20 h. After cooled, the solvent was removed with a rotary evaporator. The product in the organic layer was extracted with CHCl3 (200 mL) and water (500 mL), and dried with MgSO4. The obtained product (ethyl 6-n-dodecyloxy-2-naphthate) was then dissolved in ethanol (200 mL), to which KOH (5.62 g, 100 mmol) was slowly added and the resulting mixture was refluxed at 80 C for 5 h. After cooled to room temperature, the solvent was removed with a rotary evaporator. The resulting reddish brown oil was dissolved in water, and acetic acid (50 mL, 874 mmol) was added dropwise. The obtained white precipitate was collected, and recrystallizations from acetic acid and 2-propanol were repeated until the color of the product was completely white. The final white crystalline solid was dried under vacuum to give 3.07 g (8.61 mmol, 35 %). 1H NMR (400 MHz, CDCl3, r.t.): δ 8.63 (s, 1H, Ar-H), 8.08 (d, J = 8.8 Hz, 1H, Ar−H), 7.87 (d, J = 8.8 Hz, 1H, Ar−H), 7.77 (d, J = 8.8 Hz, 1H, Ar−H), 7.21 (d, J = 9.8 Hz, 1H, Ar−H), 7.16 (s, 1H, Ar−H), 4.11 (t, J = 6.6 Hz, 2H, OCH2), 1.86 (quin, J = 6.8 Hz, 2H, OCH2CH2), 1.47-1.20 (m, 18H, OCH2CH2(CH2)9), 0.88 (t, J = 6.3 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-dodecyloxynaphthoyl)hydrazine):S2 A mixture of 6-n-dodecyloxy-2-naphthoic acid (3.07 g, 8.61 mmol) and thionyl chloride (21 mL) was refluxed at 80 C for 3 h. After cooled to room temperature, the remaining thionyl chloride was removed thoroughly under a reduced pressure. The resulting white crystalline solid was dissolved in dry CHCl3 (100 mL), and then hydrazine monohydrate (1.25 g, 24.02 mmol) was added dropwise. After stirring for several hours, the product in the organic layer was extracted with CHCl3 (100 mL) and water (200 mL). The solvent was removed under a reduced pressure to give a white crystalline solid. The product was recrystallized from pyridine and toluene several times, yielding 1.57 g (2.21 mmol, 26 %). 1H NMR (400 MHz, CDCl3): δ 9.30 (s, 2H, CONH), 8.35 (s, 2H, Ar-H), 7.87 (d, J = 9.3 Hz, 2H, Ar−H), 7.83 (d, J = 8.8 Hz, 2H, Ar−H), 7.78 (d, J = 8.8 Hz, 2H, Ar−H), 7.22 (dd, J1 = 9.3 Hz, J2 = 2.0 Hz, 2H, Ar−H), 7.16 (d, J = 2.2 Hz, 2H, Ar−H), 4.11 (t, J = 6.6 Hz, 4H, OCH2), 1.86 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.50-1.20 (m, 36H, OCH2CH2(CH2)9), 0.88 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C46H64N2O4: C, 77.92; H, 9.10; N, 3.95. Found: C, 77.63; H, 9.21; N, 3.92 %. 1b. 1,2-Bis(4-n-hexadecyloxynaphthoyl)hydrazine (N-16) N-16 was prepared by the same procedure as described for N-12. First step (preparation of ethyl 6-hydroxy-2-naphthoate):S1 From 6-hydroxy-2-naphthoic acid (14.93 g, 79.3 mmol), yielding 14.43 g (66.8 mmol, 83 %) of a yellowish white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.54 (s, 1H, Ar-H), 8.02 (dd, J1 = 8.7 Hz, J2 = 1.6 Hz, 1H,

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Ar−H), 7.87 (d, J = 8.8 Hz, 1H, Ar−H), 7.70 (d, J = 8.5 Hz, 1H, Ar−H), 7.19 (s, 1H, Ar−H), 7.16 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz,d, 1H, Ar−H), 5.45 (s, 1H, OH), 4.43 (q, J = 7.1 Hz, 2H, COOCH2), 1.44 (t, J = 7.2 Hz, 3H, COOCH2CH3). Second step (preparation of 6-n-hexadecyloxy-2-naphthoic acid):S1 From ethyl 6-hydroxy-2-naphthoate (14.42 g, 66.8 mmol) and 1-bromo-n-hexadecane (25.14 g, 82.3 mmol), yielding 19.82 g (48.0 mmol, 73 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.62 (s, 1H, Ar-H), 8.08 (dd, J1 = 8.5 Hz, J2 = 1.7 Hz, 1H, Ar−H), 7.87 (d, J = 9.3 Hz, 1H, Ar−H), 7.77 (d, J = 8.8 Hz, 1H, Ar−H), 7.21 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H, Ar−H), 7.16 (d, J = 2.4 Hz, 1H, Ar−H), 4.11 (t, J = 6.6 Hz, 2H, OCH2), 1.87 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.47-1.25 (m, 26H, OCH2CH2(CH2)13), 0.88 (t, J = 6.8 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-hexadecyloxynaphthoyl)hydrazine):S2 From 6-n-hexadecyloxy-2-naphthoic acid (19.82 g, 48.0 mmol), recrystallized from pyridine and THF, yielding 14.64 g (17.8 mmol, 74 %) of a white crystalline solid. 1H NMR(400 MHz, pyridine-d5): δ 11.24 (s, 2H, CONH), 8.75 (s, 2H, Ar-H), 8.30 (d, J = 8.7 Hz, 2H, Ar−H), 7.84 (d, J = 8.7 Hz, 2H, Ar−H), 7.80 (d, J = 8.7 Hz, 2H, Ar−H), 7.33 (s, 2H, Ar−H), 7.29 (d, J = 9.2 Hz, 2H, Ar−H), 4.10 (t, J = 6.4 Hz, 4H, OCH2), 1.84 (quin, J = 6.9 Hz, 4H, OCH2CH2), 1.57-1.23 (m, 52H, OCH2CH2(CH2)13), 0.87 (t, J = 6.4 Hz, 6H, CH3). Elemental Anal. Calcd for C54H80N2O4: C, 78.98; H, 9.82; N, 3.41. Found: C, 78.96; H, 9.75; N, 3.41 %. 1c. 1,2-Bis(4-n-octadecyloxynaphthoyl)hydrazine (N-18) N-18 was prepared by the same procedure as described for N-12. First step (preparation of ethyl 6-hydroxy-2-naphthoate):S1 From 6-hydroxy-2-naphthoic acid (25.27 g, 134.3 mmol), yielding 28.03 g (129.5 mmol, 96 %) of a yellowish white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.53 (s, 1H, Ar-H), 8.01 (dd, J1 = 8.8 Hz, J2 = 1.5 Hz, 1H, Ar−H), 7.85 (d, J = 8.8 Hz, 1H, Ar−H), 7.73 (d, J = 8.8 Hz, 1H, Ar−H), 7.19 (s, 1H, Ar−H), 7.18 (dd, J1 = 10.5 Hz, J2 = 2.4 Hz, 1H, Ar−H), 4.44 (q, J = 7.2 Hz, 2H, COOCH2), 1.44 (t, J = 7.3 Hz, 3H, COOCH2CH3). Second step (preparation of 6-n-octadecyloxy-2-naphthoic acid):S1 From ethyl 6-hydroxy-2-naphthoate (14.00 g, 64.7 mmol) and 1-bromo-n-octadecane (25.04 g, 75.1 mmol), yielding 27.83 g (63.1 mmol, 98 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.58 (s, 1H, Ar-H), 8.04 (d, J = 8.5 Hz, 1H, Ar−H), 7.84 (d, J = 8.5 Hz, 1H, Ar−H), 7.75 (d, J = 8.5 Hz, 1H, Ar−H), 7.19 (s, 1H, Ar−H), 7.20 (dd, J1 = 9.2 Hz, J2 = 2.4 Hz, 1H, Ar−H), 7.15 (d, J = 2.4 Hz, 1H, Ar−H), 4.10 (t, J = 6.5 Hz, 2H, OCH2), 1.86 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.50 (quin, J = 7.3 Hz, 2H, OCH2CH2CH2),1.43-1.17 (m, 56H, OCH2CH2CH2(CH2)14), 0.87 (t, J = 7.0 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-octadecyloxynaphthoyl)hydrazine):S2 From 6-n-octadecyloxy-2-naphthoic acid (2.09 g,

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4.7 mmol), recrystallized from pyridine, yielding 0.80 g (0.9 mmol, 38 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.25 (s, 2H, CONH), 8.75 (s, 2H, Ar-H), 8.30 (d, J = 8.7 Hz, 2H, Ar−H), 7.84 (d, J = 8.7 Hz, 2H, Ar−H), 7.80 (d, J = 9.2 Hz, 2H, Ar−H), 7.33 (s, 2H, Ar−H), 7.29 (d, J = 9.2 Hz, 2H, Ar−H), 4.10 (t, J = 6.6 Hz, 4H, OCH2), 1.83 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.56-1.20 (m, 60H, OCH2CH2(CH2)15), 0.87 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C58H88N2O4: C, 79.36; H, 10.35; N, 3.21. Found: C, 79.40; H, 10.11; N, 3.19 %.

1d. 1,2-Bis(4-n-eicosyloxynaphthoyl)hydrazine (N-20) N-20 was prepared by the same procedure as described for N-12. Second step (preparation of 6-n-eicosyloxy-2-naphthoic acid):S1 From ethyl 6-hydroxy-2-naphthoate (14.03 g, 64.9 mmol) and 1-bromo-n-eicosane (26.56 g, 73.5 mmol), yielding 26.90 g (57.4 mmol, 88 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.60 (s, 1H, Ar-H), 8.06 (dd, J1 = 8.8 Hz, J2 = 1.5 Hz, 1H, Ar−H), 7.85 (d, J = 9.3 Hz, 1H, Ar−H), 7.75 (d, J = 8.8 Hz, 1H, Ar−H), 7.20 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H, Ar−H), 7.16 (d, J = 2.4 Hz, 1H, Ar−H), 4.11 (t, J = 6.6 Hz, 2H, OCH2), 1.86 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.56-1.20 (m, 34H, OCH2CH2(CH2)17), 0.88 (t, J = 6.6 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-eicosyloxynaphthoyl)hydrazine):S2 From 6-n-eicosyloxy-2-naphthoic acid (9.64 g, 20.6 mmol), recrystallized from pyridine and THF, yielding 3.62 g (3.88 mmol, 19 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): 8.75 (s, 2H, Ar-H), 8.30 (d, J = 8.7 Hz, 2H, Ar−H), 7.84 (d, J = 8.7 Hz, 2H, Ar−H), 7.80 (d, J = 9.2 Hz, 2H, Ar−H), 7.33 (s, 2H, Ar−H), 7.29 (d, J = 8.7 Hz, 2H, Ar−H), 4.10 (t, J = 6.4 Hz, 4H, OCH2), 1.84 (quin, J = 6.8 Hz, 4H, OCH2CH2), 1.58-1.23 (m, 68H, OCH2CH2(CH2)17), 0.87 (t, J = 6.9 Hz, 6H, CH3). Elemental Anal. Calcd for C62H96N2O4: C, 79.78; H, 10.37; N, 3.00. Found: C, 79.52; H, 10.67; N, 2.98 %.

1e. 1,2-Bis(4-n-docosyloxynaphthoyl)hydrazine (N-22) N-22 was prepared by the same procedure as described for N-12. First step (preparation of ethyl 6-hydroxy-2-naphthoate):S1 From 6-hydroxy-2-naphthoic acid (10.07 g, 53.5 mmol), yielding 11.42 g (52.9 mmol, 99 %) of a yellowish white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.54 (s, 1H, Ar-H), 8.02 (d, J = 8.3 Hz, 1H, Ar−H), 7.86 (d, J = 8.3 Hz, 1H, Ar−H), 7.70 (d, J = 8.8 Hz, 1H, Ar−H), 7.19 (s, 1H, Ar−H), 7.17 (d, J = 10.2 Hz, 1H, Ar−H), 5.59 (s, 1H, OH), 4.44 (q, J = 7.2 Hz, 2H, COOCH2), 1.44 (t, J = 7.1 Hz, 3H, COOCH2CH3). Second step (preparation of 6-n-docosyloxy-2-naphthoic acid):S1 From ethyl 6-hydroxy-2-naphthoate (5.72 g, 26.5 mmol) and 1-bromo-n-docosane (7.02 g, 18.0 mmol), yielding 3.45 g (6.94 mmol, 39 %) of a white crystalline

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solid. 1H NMR (400 MHz, CDCl3): δ 8.58 (s, 1H, Ar-H), 8.04 (d, J = 7.8 Hz, 1H, Ar−H), 7.84 (d, J = 9.3 Hz, 1H, Ar−H), 7.75 (d, J = 8.3 Hz, 1H, Ar−H), 7.20 (dd, J1 = 9.0 Hz, J2 = 2.2 Hz, 1H, Ar−H), 7.16 (s, 1H, Ar−H), 4.11 (t, J = 6.6 Hz, 2H, OCH2), 1.86 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.55-1.23 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.8 Hz, 3H, CH3). ). Third step (preparation of 1,2-Bis(4-n-docosyloxynaphthoyl)hydrazine):S2 From 6-n-docosyloxy-2-naphthoic acid (3.45 g, 6.94 mmol), recrystallized from pyridine and THF, yielding 1.77 g (1.68 mmol, 24 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 9.24 (s, 2H, CONH), 8.35 (s, 2H, Ar-H), 7.88 (d, J = 8.3 Hz, 2H, Ar−H), 7.85 (d, J = 8.3 Hz, 2H, Ar−H), 7.80 (d, J = 7.4 Hz, 2H, Ar−H), 7.17 (s, 4H, Ar−H), 4.11 (t, J = 6.6 Hz, 4H, OCH2), 1.86 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.55-1.20 (m, 76H, OCH2CH2(CH2)19), 0.88 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C66H104N2O4: C, 80.11; H, 10.59; N, 2.83. Found: C, 80.05; H, 10.81; N, 2.68 %. 2a. 1,2-Bis(4-n-decyloxyphenylbenzoyl)hydrazine (PB-10) First step (preparation of ethyl 4-hydroxybiphenyl carboxylate):S3 4-Hydroxybipheyl carboxylic acid (25.34 g, 118.3 mmol) was dissolved in ethanol (400 mL), to which concentrated H2SO4 (13.19 g, 134.5 mmol) was added dropwise. The mixture was then refluxed at 80 C for 50 h. After cooled, the solvent was removed with a rotary evaporator. The product in the organic layer was extracted with CHCl3 (200 mL) and K2CO3 (15.27 g, 110.5 mmol) aqueous solution, and washed with water thoroughly until neutral. After that, the solvent was dried with MgSO4 and the solvent was removed under a reduced pressure to give a white crystalline solid, identified by 1H NMR. Yield 25.32 g (104.5 mmol), 88 %. 1H NMR (400 MHz, CDCl3): δ 8.08 (d, J = 8.3 Hz, 2H, Ar-H), 7.61 (d, J = 8.3 Hz, 2H, Ar−H), 7.53 (d, J = 8.8 Hz, 2H, Ar−H), 6.97 (d, J = 8.3 Hz, 2H, Ar−H), 5.40 (s, broad, 1H, OH), 4.41 (q, J = 7.1 Hz, 2H, COOCH2), 1.42 (t, J = 6.8 Hz, 3H, COOCH2CH3). Second step (preparation of 4-n-decyloxybiphenyl carboxylic acid):S3 Ethyl 4-hydroxybiphenyl carboxylate (8.48 g, 35.0 mmol), 1-bromo-n-decane (11.12 g, 50.3 mmol), and K2CO3 (10.50 g, 76.0 mmol) were dissolved in acetone (300 mL), and stirred at 60 C for 24 h. After cooled, the solvent was removed with a rotary evaporator. The obtained product was dissolved in ethanol (200 mL), to which NaOH (6.62 g, 165.7 mmol) dissolved in ethanol (100 mL) was slowly added and the resulting mixture was stirred under reflux at 80 C for 27 h. After cooled to room temperature, the precipitate was collected and washed with small amount of ethanol, THF, and water. The product was recrystallized twice from acetic acid (200 mL), and finally dried under vacuum to give 9.53 g (24.91 mmol, 57 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3):

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δ 8.14 (d, J = 6.8 Hz, 2H, Ar-H), 7.65 (d, J = 6.8 Hz, 2H, Ar−H), 7.56 (d, J = 8.8 Hz, 2H, Ar−H), 6.97 (d, J = 8.8 Hz, 2H, Ar−H), 4.01 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.50-1.20 (m, 14H, OCH2CH2(CH2)7), 0.89 (t, J = 6.8 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-decyloxyphenylbenzoyl)hydrazine):S2 A mixture of 4-n-decyloxybiphenyl carboxylic acid (6.20 g, 17.49 mmol) and thionyl chloride (22 mL) was refluxed at 80 C for 3.5 h. After cooled to room temperature, the remaining thionyl chloride was removed thoroughly under a reduced pressure. The resulting white crystalline solid was dissolved in dry CHCl3 (100 mL), and then hydrazine monohydrate (0.78 g, 15.59 mmol) was added dropwise. After stirring for 1 h, the reaction mixture was evaporated to dryness and washed with water (50 mL), to which CHCl3 was added and the product in the organic layer was extracted. The solvent was removed under a reduced pressure to give a white solid. The solid was washed with THF, and recrystallized from boiled pyridine twice, yielding 0.56 g (0.79 mmol, 5 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.15 (s, 2H, CONH), 8.28 (d, J = 7.3 Hz, 4H, Ar-H), 7.69 (d, J = 7.3 Hz, 4H, Ar-H), 7.64 (d, J = 8.3 Hz, 4H, Ar-H), 7.11 (d, J = 7.8 Hz, 4H, Ar-H), 4.03 (t, J = 7.4 Hz, 4H, OCH2), 1.78 (m, 4H, OCH2CH2), 1.48-1.25 (m, 28H, OCH2CH2(CH2)7), 0.87 (s, broad, 6H, CH3). Elemental Anal. Calcd for C46H60N2O4: C, 78.23; H, 8.77; N, 4.01. Found: C, 78.37; H, 8.58; N, 3.97 %. 2b. 1,2-Bis(4-n-dodecyloxyphenylbenzoyl)hydrazine (PB-12) PB-12 was prepared by the same procedure as described for PB-10. First step (preparation of ethyl 4-hydroxybiphenyl carboxylate):S3 From 4-hydroxybipheyl carboxylic acid (5.00 g, 23.3 mmol), yielding 4.57 g (18.9 mmol, 81 %) of a white solid. 1H NMR (400 MHz, CDCl3): δ 8.08 (d, J = 8.0 Hz, 2H, Ar-H), 7.61 (d, J = 8.3 Hz, 2H, Ar−H), 7.52 (d, J = 8.6 Hz, 2H, Ar−H), 6.94 (d, J = 8.5 Hz, 2H, Ar−H), 5.28 (s, broad, 1H, OH), 4.40 (q, J = 7.2 Hz, 2H, COOCH2), 1.42 (t, J = 7.2 Hz, 3H, COOCH2CH3). Second step (preparation of 4-n-dodecyloxybiphenyl carboxylic acid):S3 From ethyl 4-hydroxybiphenyl carboxylate (4.57 g, 18.9 mmol) and 1-bromo-n-dodecane (6.08 g, 24.4 mmol), yielding 2.69 g (6.65 mmol, 36 %) of a white crystalline solid. 1H NMR (400 MHz, THF-d8): δ 11.34 (s, broad, 1H, OH), 8.04 (d, J = 8.3 Hz, 2H, Ar-H), 7.64 (d, J = 8.8 Hz, 2H, Ar−H), 7.58 (d, J = 8.8 Hz, 2H, Ar−H), 6.97 (d, J = 8.8 Hz, 2H, Ar−H), 4.00 (t, J = 6.3 Hz, 2H, OCH2), 1.79 (quin, J = 7.2 Hz, 2H, OCH2CH2), 1.40-1.20 (m, 18H, OCH2CH2(CH2)9), 0.89 (t, J = 6.8 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-dodecyloxyphenylbenzoyl)hydrazine):S2 From 4-n-dodecyloxybiphenyl carboxylic acid (2.69 g, 6.65 mmol), recrystallized from boiled pyridine and toluene several times, yielding 2.62 g (3.44 mmol, 52 %) of a white crystalline solid. 1H NMR (400 MHz,

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toluene-d8): δ 8.72 (s, 2H, CONH), 7.74 (d, J = 8.0 Hz, 4H, Ar-H), 7.40 (d, J = 8.5 Hz, 8H, Ar−H), 6.91 (d, J = 8.8 Hz, 4H, Ar−H), 3.84 (t, J = 6.4 Hz, 4H, OCH2), 1.73 (quin, J = 7.6 Hz, 4H, OCH2CH2), 1.48-1.25 (m, 36H, OCH2CH2(CH2)9), 0.92 (t, J = 6 Hz, 6H, CH3). Elemental Anal. Calcd for C50H68N2O4: C, 78.63; H, 9.20; N, 3.67. Found: C, 78.90; H, 9.01; N, 3.68 %.

2c. 1,2-Bis(4-n-tetradecyloxyphenylbenzoyl)hydrazine (PB-14) PB-14 was prepared by the same procedure as described for PB-10. Second step (preparation of 4-n-tetradecyloxybiphenyl carboxylic acid):S3 1H NMR (400 MHz, THF-d8): δ 8.12 (d, J = 8.3 Hz, 2H, Ar-H), 7.64 (d, J = 8.3 Hz, 2H, Ar−H), 7.55 (d, J = 8.3 Hz, 2H, Ar−H), 6.98 (d, J = 8.3 Hz, 2H, Ar−H), 4.01 (t, J = 6.6 Hz, 2H, OCH2), 1.80 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.55-1.20 (m, 22H, OCH2CH2(CH2)11), 0.88 (t, J = 6.8 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-tetradecyloxyphenylbenzoyl)hydrazine):S2 From 4-n-tetradecyloxybiphenyl carboxylic acid (1.94 g, 4.72 mmol), recrystallized from boiled pyridine and toluene several times, yielding 0.80 g (0.98 mmol, 21 %) of a white crystalline solid. 1H NMR (400 MHz, toluene-d8): δ 8.74 (s, 2H, CONH), 7.75 (d, J = 8.3 Hz, 4H, Ar-H), 7.40 (d, J = 7.3 Hz, 8H, Ar−H), 6.91 (d, J = 8.3 Hz, 4H, Ar−H), 3.85 (t, J = 6.3 Hz, 4H, OCH2), 1.73 (quin, J = 6.7 Hz, 4H, OCH2CH2), 1.48-1.25 (m, 44H, OCH2CH2(CH2)11), 0.91 (t, J = 6.7 Hz, 6H, CH3). Elemental Anal. Calcd for C54H76N2O4: C, 79.37; H, 9.37; N, 3.43. Found: C, 79.11; H, 9.37; N, 3.44 %.

2d. 1,2-Bis(4-n-hexatradecyloxyphenylbenzoyl)hydrazine (PB-16) PB-16 was prepared by the same procedure as described for PB-10. Second step (preparation of 4-n-hexadecyloxybiphenyl carboxylic acid):S3 1H NMR (400 MHz, THF-d8): δ 8.11(d, J = 8.3 Hz, 2H, Ar-H), 7.63 (d, J = 8.3 Hz, 2H, Ar−H), 7.55 (d, J = 8.8 Hz, 2H, Ar−H), 6.98 (d, J = 8.8 Hz, 2H, Ar−H), 4.01 (t, J = 6.3 Hz, 2H, OCH2), 1.81 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.50-1.20 (m, 26H, OCH2CH2(CH2)13), 0.88 (t, J = 7.3 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-hexadecyloxyphenylbenzoyl)hydrazine):S2 From 4-n-hexadecyloxybiphenyl carboxylic acid (2.78 g, 6.34 mmol), recrystallized from boiled pyridine and toluene several times, yielding 1.64 g (1.88 mmol, 30 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 8.29 (d, J = 8.2 Hz, 4H, Ar-H), 7.69 (d, J = 8.2 Hz, 4H, Ar−H), 7.62 (d, J = 8.7 Hz, 4H, Ar−H), 7.10 (d, J = 8.7 Hz, 4H, Ar−H), 4.04 (t, J = 6.4 Hz, 4H, OCH2), 1.79 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.55-1.23 (m, 60H, OCH2CH2(CH2)13), 0.87 (t, J = 6.9 Hz, 6H, CH3). Elemental Anal. Calcd for C58H84N2O4: C, 79.76; H, 9.70; N, 3.21. Found: C, 79.53; H, 9.83; N, 3.30 %.

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2e. 1,2-Bis(4-n-octadecyloxyphenylbenzoyl)hydrazine (PB-18) PB-18 was prepared by the same procedure as described for PB-10. Second step (preparation of 4-n-octadecyloxybiphenyl carboxylic acid):S3 From ethyl 4-hydroxybiphenyl carboxylate (10.55 g, 43.5 mmol) and 1-bromo-n-octadecane (16.69 g, 50.1 mmol), yielding 12.08 g (25.88 mmol, 59 %) of a white crystalline solid. 1H NMR (400 MHz, THF-d8): δ 8.10 (d, J = 8.3 Hz, 2H, Ar-H), 7.63 (d, J = 7.8 Hz, 2H, Ar−H), 7.55 (d, J = 7.8 Hz, 2H, Ar−H), 6.98 (d, J = 8.3 Hz, 2H, Ar−H), 4.01 (t, J = 6.6 Hz, 2H, OCH2), 1.80 (quin, J = 6.7 Hz, 2H, OCH2CH2), 1.50-1.20 (m, 26H, OCH2CH2(CH2)15), 0.88 (t, J = 6.6 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-hexadecyloxyphenylbenzoyl)hydrazine):S2 From 4-n-octadecyloxybiphenyl carboxylic acid (9.34 g, 20.01 mmol), recrystallized from boiled pyridine and toluene several times, yielding 2.03 g (2.18 mmol, 22 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.17 (s, 2H, CONH), 8.29 (d, J = 8.2 Hz, 4H, Ar-H), 7.70 (d, J = 8.2 Hz, 4H, Ar−H), 7.62 (d, J = 8.7 Hz, 4H, Ar−H), 7.10 (d, J = 8.7 Hz, 4H, Ar−H), 4.04 (t, J = 6.4 Hz, 4H, OCH2), 1.81 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.55-1.22 (m, 60H, OCH2CH2(CH2)15), 0.87 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C62H92N2O4: C, 80.12; H, 9.98; N, 3.01. Found: C, 80.43; H, 10.34; N, 3.07 %. 2f. 1,2-Bis(4-n-nonadecyloxyphenylbenzoyl)hydrazine (PB-19) PB-19 was prepared by the same procedure as described for PB-10. Second step (preparation of 4-n-nonadecyloxybiphenyl carboxylic acid):S3 1H NMR (400 MHz, CDCl3): δ 8.10 (d, J = 8.3 Hz, 2H, Ar-H), 7.63 (d, J = 8.3 Hz, 2H, Ar−H), 7.55 (d, J = 8.8 Hz, 2H, Ar−H), 6.98 (d, J = 8.8 Hz, 2H, Ar−H), 4.01 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.50-1.20 (m, 32H, OCH2CH2(CH2)16), 0.88 (t, J = 6.6 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-nonadecyloxyphenylbenzoyl)hydrazine):S2 From 4-n-nonadecyloxybiphenyl carboxylic acid (2.08 g, 4.33 mmol), recrystallized from boiled pyridine several times, yielding 1.03 g (1.08 mmol, 25 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.11 (s, 2H, CONH), 8.28 (d, J = 8.3 Hz, 4H, Ar-H), 7.69 (d, J = 8.3 Hz, 4H, Ar−H), 7.62 (d, J = 8.8 Hz, 4H, Ar−H), 7.09 (d, J = 8.3 Hz, 4H, Ar−H), 4.04 (t, J = 6.3 Hz, 4H, OCH2), 1.80 (quin, J = 6.8 Hz, 4H, OCH2CH2), 1.60-1.20 (m, 64H, OCH2CH2(CH2)16), 0.87 (t, J = 6.3 Hz, 6H, CH3). Elemental Anal. Calcd for C64H96N2O4: C, 80.28; H, 10.11; N, 2.93. Found: C, 80.20; H, 10.48; N, 2.96 %. 2g. 1,2-Bis(4-n-eicosyloxyphenylbenzoyl)hydrazine (PB-20)

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PB-20 was prepared by the same procedure as described for PB-10. Second step (preparation of 4-n-eicosyloxybiphenyl carboxylic acid):S3 From ethyl 4-hydroxybiphenyl carboxylate (13.84 g, 57.1 mmol) and 1-bromo-n-eicosane (21.55 g, 59.6 mmol), yielding 19.01 g (38.42 mmol, 67 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 8.11 (d, J = 8.3 Hz, 2H, Ar-H), 7.63 (d, J = 8.3 Hz, 2H, Ar−H), 7.55 (d, J = 8.3 Hz, 2H, Ar−H), 6.98 (d, J = 8.3 Hz, 2H, Ar−H), 4.01 (t, J = 6.6 Hz, 2H, OCH2), 1.80 (quin, J = 6.8 Hz, 2H, OCH2CH2), 1.60-1.20 (m, 34H, OCH2CH2(CH2)17), 0.88 (t, J = 6.3 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-eicosyloxyphenylbenzoyl)hydrazine):S2 From 4-n-eicosyloxybiphenyl carboxylic acid (3.50 g, 7.08 mmol), recrystallized from boiled pyridine two times, yielding 0.57 g (0.59 mmol, 8 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 8.30 (d, J = 8.2 Hz, 4H, Ar-H), 7.70 (d, J = 8.2 Hz, 4H, Ar−H), 7.62 (d, J = 8.7 Hz, 4H, Ar−H), 7.10 (d, J = 8.7 Hz, 4H, Ar−H), 4.04 (t, J = 6.4 Hz, 4H, OCH2), 1.81 (quin, J = 6.9 Hz, 4H, OCH2CH2), 1.57-1.23 (m, 68H, OCH2CH2(CH2)17), 0.87 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C66H100N2O4: C, 80.44; H, 10.23; N, 2.84. Found: C, 79.87; H, 10.50; N, 2.83 %. 2h. 1,2-Bis(4-n-heneicosyloxyphenylbenzoyl)hydrazine (PB-21) PB-21 was prepared by the same procedure as described for PB-10. Second step (preparation of 4-n-heneicosyloxybiphenyl carboxylic acid):S3 1H NMR (400 MHz, CDCl3): δ 8.10 (d, J = 7.3 Hz, 2H, Ar-H), 7.63 (d, J = 7.8 Hz, 2H, Ar−H), 7.55 (d, J = 8.8 Hz, 2H, Ar−H), 6.98 (d, J = 9.2 Hz, 2H, Ar−H), 4.01 (t, J = 6.6 Hz, 2H, OCH2), 1.80 (quin, J = 6.7 Hz, 2H, OCH2CH2), 1.6-1.2 (m, 36H, OCH2CH2(CH2)18), 0.89 (t, J = 5.7 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-heneicosyloxyphenylbenzoyl)hydrazine):S2 From 4-n-heneicosyloxybiphenyl carboxylic acid (2.05 g, 4.03 mmol), recrystallized from boiled pyridine and toluene several times, yielding 1.18 g (1.16 mmol, 29 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.17 (s, 2H, CONH), 8.29 (d, J = 8.2 Hz, 4H, Ar-H), 7.70 (d, J = 8.7 Hz, 4H, Ar−H), 7.62 (d, J = 8.7 Hz, 4H, Ar−H), 7.10 (d, J = 8.7 Hz, 4H, Ar−H), 4.04 (t, J = 6.6 Hz, 4H, OCH2), 1.81 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.55-1.20 (m, 72H, OCH2CH2(CH2)18), 0.87 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C68H104N2O4: C, 80.58; H, 10.34; N, 2.76. Found: C, 80.21; H, 10.64; N, 2.78 %. 2i. 1,2-Bis(4-n-docosyloxyphenylbenzoyl)hydrazine (PB-22) PB-22 was prepared by the same procedure as described for PB-10. First step (preparation of ethyl 4-hydroxybiphenyl carboxylate):S3 From 4-hydroxybipheyl

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carboxylic acid (5.01 g, 23.3 mmol), yielding 4.39 g (18.1 mmol, 78 %) of a white solid. 1H NMR (400 MHz, CDCl3): δ 8.08 (d, J = 8.8 Hz, 2H, Ar-H), 7.60 (d, J = 8.3 Hz, 2H, Ar−H), 7.51 (d, J = 8.8 Hz, 2H, Ar−H), 6.95 (d, J = 8.3 Hz, 2H, Ar−H), 6.59 (s, broad, 1H, OH), 4.40 (q, J = 7.2 Hz, 2H, COOCH2), 1.41 (quin, J = 7.3 Hz, 3H, COOCH2CH3). Second step (preparation of 4-n-docosyloxybiphenyl carboxylic acid):S3 From ethyl 4-hydroxybiphenyl carboxylate (4.39 g, 18.1 mmol) and 1-bromo-n-docosane (9.18 g, 23.6 mmol), yielding 7.12 g (13.6 mmol, 75 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3, 50 C): δ 8.10 (d, J = 7.3 Hz, 2H, Ar-H), 7.63 (d, J = 8.3 Hz, 2H, Ar−H), 7.55 (d, J = 9.0 Hz, 2H, Ar−H), 6.98 (d, J = 8.3 Hz, 2H, Ar−H), 4.01 (t, J = 6.4 Hz, 2H, OCH2), 1.81 (quin, J = 6.9 Hz, 2H, OCH2CH2), 1.40-1.20 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.6 Hz, 3H, CH3). Third step (preparation of 1,2-Bis(4-n-docosyloxyphenylbenzoyl)hydrazine):S2 From 4-n-docosyloxybiphenyl carboxylic acid (7.12 g, 13.6 mmol), recrystallized from boiled pyridine and toluene several times, yielding 0.43 g (0.41 mmol, 3 %) of a white crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 8.64 (s, 2H, CONH), 8.29 (d, J = 7.8 Hz, 4H, Ar-H), 7.70 (d, J = 7.3 Hz, 4H, Ar−H), 7.62 (d, J = 8.7 Hz, 4H, Ar−H), 7.10 (d, J = 6.4 Hz, 4H, Ar−H), 4.04 (t, J = 6.4 Hz, 4H, OCH2), 1.81 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.56-1.22 (m, 76H, OCH2CH2(CH2)19), 0.88 (t, J = 6.4 Hz, 6H, CH3). Elemental Anal. Calcd for C70H108N2O4: C, 80.72; H, 10.45; N, 2.69. Found: C, 80.64; H, 10.25; N, 2.75 %. 3a. 1,2-Bis(4-n-hexadecyloxystilbenecarbonyl)hydrazine (S-16) First step (preparation of 4-hexadecyloxybenzaldehyde): 4-hydroxybenzaldehyde (12.21 g, 100 mmol), 1-bromo-n-hexadecane (30.53 g, 100 mmol), and K2CO3 (13.82 g, 100 mmol) were dissolved in acetone (200 mL), and refluxed for 29 h, to which K2CO3 (13.83 g, 100 mmol) was added and refluxed for further 24 h. After cooled, the solvent was removed with a rotary evaporator. The product in the organic layer was extracted with CHCl3 and water, and the solvent was removed under a reduced pressure to give a yellowish white solid. The crude product was recrystallized from ethanol, dried under vacuum, identified by 1H NMR. Yield 27.39 g (79.0 mmol), 79 %. 1H NMR (400 MHz, CDCl3): δ 9.88 (s, CHO), 7.83 (d, J = 8.3 Hz, 2H, Ar−H), 6.99 (d, J = 8.8 Hz, 2H, Ar−H), 4.04 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.20-1.52 (m, 26H, OCH2CH2(CH2)13), 0.88 (t, J = 6.8 Hz, 3H, CH3). Second step (preparation of (4-methoxycarbonylbenzyl)triphenylphosphonium bromide): 4-methoxycarbonylbenzylbromide (2.00 g, 8.73 mmol) and triphenylphosphine (3.90 g, 14.87 mmol) were dissolved in dry xylene (150 mL) and refluxed for 20 h under N2 atmosphere. After cooled to room temperature, the precipitate was collected. The crude product was recrystallized from toluene-CHCl3 (1:1), dried in vacuum for 14 h, identified

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by 1H NMR. Yield 4.51 g (9.19 mmol), 91 %. 1H NMR (400 MHz, CDCl3): δ 7.53-7.90 (m, 15H, CH2Ar−H), 7.23 (dd, J1 = 7.8 Hz, J2 = 2.0 Hz, 4H, CH3OCOAr−H), 5.70 (d, J = 15.6 Hz, 2H, Ar−CH2), 3.87 (s, 3H, COOCH3). Third step (preparation of 4-n-hexadecyloxystilbenecarboxylic acid): (4-methoxycarbonylbenzyl)-triphenylphosphonium bromide (4.21 g, 8.57 mmol) and K2CO3 (6.80 g, 49.2 mmol) were dissolved in dry THF-CH2Cl2 (2:1) 150 mL, to which 4-hexadecyloxybenzaldehyde (3.25 g, 9.41 mmol) was slowly added and refluxed for 46.5 h under N2 atmosphere. After cooled to room temperature, the precipitate was collected and washed with water. The crude product was recrystallized from THF, dried in vacuum. The obtained product (2.30 g, 4.81 mmol) and KOH (1.12 g, 20.0 mmol) were each dissolved in ethanol (50 mL), and both were mixed, refluxed for 26.5 h. After that, the solution was acidified with HCl (1.85 mL). After cooled, the precipitate was collected, twice recrystallized from acetic acid, finally dried under vacuum, identified by 1H NMR. Yield 2.14 g (4.61 mmol), 54 %. 1H NMR (400 MHz, CDCl3): δ 8.03 (d, J = 8.2 Hz, 2H, Ar−H), 7.54 (d, J = 8.2 Hz, 2H, Ar−H), 7.45 (d, J = 9.2 Hz, 2H, Ar−H), 7.17 (d, J = 17.0 Hz, 1H, −CH=), 6.98 (d, J = 16.5 Hz, 1H, −CH=), 6.89 (d, J = 8.7 Hz, 2H, Ar−H), 3.98 (t, J = 6.6 Hz, 2H, OCH2), 1.78 (quin, J = 6.6 Hz, 2H, OCH2CH2), 1.26 (m, 26H, OCH2CH2(CH2)13), 0.88 (t, J = 7.1 Hz, 3H, CH3). Fourth step (1,2-Bis(4-n-hexadecyloxystilbenecarbonyl)hydrazine): 4-n-hexadecyloxystilbenecarboxylic acid (0.95 g, 2.05 mmol) was dissolved in dry toluene (20 mL) under N2 atmosphere, to which three drops of DMF and oxalyl chloride (0.17 mL, 2.01 mmol) were added and refluxed for 2h. After that, the solvent was removed under a reduced pressure. The obtained chloride was dissolved in dry toluene (20 mL) under N2 atmosphere, to which hydrazine monohydrate (0.1 mL) was added and refluxed at 100 C for 2 h. After cooled to room temperature, the precipitate was collected, recrystallized twice from pyridine, washed with THF, finally dried in vacuum, affording a final product. Yield 0.27 g (0.29 mmol, 29 %). 1H NMR (400 MHz, pyridine-d5): δ 8.23 (d, J = 8.7 Hz, 4H, Ar−H), 7.59 (d, J = 8.2 Hz, 4H, Ar−H), 7.54 (d, J = 8.7 Hz, 4H, Ar−H), 7.26 (d, J = 16.0 Hz, 2H, −CH=), 7.10 (d, J = 16.5 Hz, 2H, −CH=), 7.04 (d, J = 8.7 Hz, 4H, Ar−H), 4.01 (t, J = 6.4 Hz, 4H, OCH2), 1.79 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.33 (m, 52H, OCH2CH2(CH2)13), 0.87 (t, J = 6.6 Hz, 3H, CH3). Elemental Anal. Calcd for C62H88N2O4: C, 80.45; H, 9.60; N, 3.03. Found: C, 80.20; H, 9.81; N, 2.97 %.

3b. 1,2-Bis(4-n-octadecyloxystilbenecarbonyl)hydrazine (S-18) S-18 was prepared by the same procedure as described for S-16. First step (preparation

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of 4-octadecyloxybenzaldehyde): 1H NMR (400 MHz, CDCl3): δ 9.88 (s, CHO), 7.83 (d, J = 8.8 Hz, 2H, Ar−H), 6.99 (d, J = 8.8 Hz, 2H, Ar−H), 4.04 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.20-1.50 (m, 30H, OCH2CH2(CH2)15), 0.88 (t, J = 6.6 Hz, 3H, CH3). Third step (preparation of 4-n-octadecyloxystilbenecarboxylic acid): From (4-methoxycarbonylbenzyl)triphenylphosphonium bromide (4.04 g, 8.23 mmol) and 4-octadecyloxybenzaldehyde (2.63 g, 7.02 mmol), recrystallized twice from acetic acid, yielding 2.03 g (4.12 mmol, 59 %). 1H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 8.7 Hz, 2H, Ar−H), 7.54 (d, J = 8.3 Hz, 2H, Ar−H), 7.45 (d, J = 8.7 Hz, 2H, Ar−H), 7.18 (d, J = 14.6 Hz, 1H, −CH=), 6.99 (d, J = 9.2 Hz, 1H, −CH=), 6.89 (d, J = 8.7 Hz, 2H, Ar−H), 3.98 (t, J = 6.9 Hz, 2H, OCH2), 1.80 (quin, J = 6.6 Hz, 2H, OCH2CH2), 1.26 (m, 30H, OCH2CH2(CH2)15), 0.88 (t, J = 6.9 Hz, 3H, CH3). Fourth step (1,2-Bis(4-n-octadecyloxystilbenecarbonyl)hydrazine): From 4-n-octadecyloxystilbenecarboxylic acid (1.00 g, 2.03 mmol), recrystallized from pyridine three times, washed with THF, yielding 0.38 g (0.39 mmol, 38%). 1H NMR (400 MHz, pyridine-d5): δ 8.23 (d, J = 8.2 Hz, 4H, Ar−H), 7.59 (d, J = 8.3 Hz, 4H, Ar−H), 7.55 (d, J = 8.7 Hz, 4H, Ar−H), 7.27 (d, J = 16.5 Hz, 2H, −CH=), 7.10 (d, J = 16.5 Hz, 2H, −CH=), 7.04 (d, J = 8.7 Hz, 4H, Ar−H), 4.01 (t, J = 6.4 Hz, 4H, OCH2), 1.79 (quin, J = 6.7 Hz, 4H, OCH2CH2), 1.34 (m, 60H, OCH2CH2(CH2)15), 0.88 (t, J = 6.9 Hz, 3H, CH3). Elemental Anal. Calcd for C66H96N2O4: C, 80.74; H, 9.88; N, 2.85. Found: C, 80.66; H, 9.98; N, 2.79 %. 3c. 1,2-Bis(4-n-eicosyloxystilbenecarbonyl)hydrazine (S-20) S-20 was prepared by the same procedure as described for S-16. First step (preparation of 4-eicosyloxybenzaldehyde): From 4-hydroxybenzaldehyde (2.56 g, 21.0 mmol) and 1-bromo-n-eicosane (6.44 g, 17.8 mmol), recrystallized from acetone, yielding 4.26 g (10.7 mmol, 60 %). 1H NMR (400 MHz, CDCl3): δ 9.87 (s, CHO), 7.81 (d, J = 9.2 Hz, 2H, Ar−H), 6.98 (d, J = 8.7 Hz, 2H, Ar−H), 4.02 (t, J = 6.8 Hz, 2H, OCH2), 1.80 (quin, J = 11.1 Hz, 2H, OCH2CH2), 1.24 (m, 34H, OCH2CH2(CH2)17), 0.87 (t, J = 7.3 Hz, 3H, CH3). Second step (preparation of (4-methoxycarbonylbenzyl)triphenylphosphonium bromide): From 4-methoxycarbonylbenzylbromide (4.63 g, 20.2 mmol), purified by column chromatography with chloroform as the eluent, yielding 9.76 g (19.9 mmol, 98%). 1H NMR (400 MHz, CDCl3): δ 7.53-7.80 (m, 15H, CH2Ar−H), 7.20 (dd, J1 = 8.7 Hz, J2 = 2.7 Hz, 4H, CH3OCOAr−H), 5.65 (d, J = 15.6 Hz, 2H, Ar−CH2), 3.83 (s, 3H, COOCH3). Third step (preparation of 4-n-eicosyloxystilbenecarboxylic acid): From (4-methoxycarbonylbenzyl)triphenylphosphonium bromide (5.46 g, 11.1 mmol) and 4-eicosyloxybenzaldehyde (4.26 g, 10.7 mmol), recrystallized twice from acetic acid, yielding 2.38 g (4.57 mmol, 53%). 1H NMR (400 MHz, CDCl3): δ 8.03 (d, J = 8.3 Hz, 2H, Ar−H), 7.54 (d, J = 9.2 Hz, 2H, Ar−H), 7.45 (d, J = 9.2 Hz, 2H, Ar−H), 7.17 (d, J =

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15.8 Hz, 1H, −CH=), 6.98 (d, J = 16.9 Hz, 1H, −CH=), 6.89 (d, J = 8.7 Hz, 2H, Ar−H), 3.98 (t, J = 6.4 Hz, 2H, OCH2), 1.79 (quin, J = 9.1 Hz, 2H, OCH2CH2), 1.26 (m, 34H, OCH2CH2(CH2)17), 0.88 (t, J = 6.4 Hz, 3H, CH3). Fourth step (1,2-Bis(4-n-eicosyloxystilbenecarbonyl)hydrazine): From 4-n-eicosyloxystilbenecarboxylic acid (1.01 g, 1.94 mmol), recrystallized from pyridine four times, washed with THF, yielding 0.47 g (0.45 mmol, 47%). 1H NMR (400 MHz, pyridine-d5): δ 8.23 (d, J = 8.2 Hz, 4H, Ar−H), 7.59 (d, J = 8.2 Hz, 4H, Ar−H), 7.55 (d, J = 8.7 Hz, 4H, Ar−H), 7.27 (d, J = 16.5 Hz, 2H, −CH=), 7.10 (d, J = 16.0 Hz, 2H, −CH=), 7.04 (d, J = 8.7 Hz, 4H, Ar−H), 4.02 (t, J = 6.4 Hz, 4H, OCH2), 1.79 (quin, J = 6.7 Hz, 4H, OCH2CH2), 1.34 (m, 68H, OCH2CH2(CH2)17), 0.88 (t, J = 7.1 Hz, 3H, CH3). Elemental Anal. Calcd for C70H104N2O4: C, 81.01; H, 10.12; N, 2.70. Found: C, 81.52; H, 10.33; N, 2.79 %.

3d. 1,2-Bis(4-n-docosyloxystilbenecarbonyl)hydrazine (S-22) S-22 was prepared by the same procedure as described for S-16. First step (preparation of 4-docosyloxybenzaldehyde): From 4-hydroxybenzaldehyde (3.11 g, 25.5 mmol) and 1-bromo-n-docosane (11.73 g, 30.1 mmol), purified by column chromatography with chloroform-hexane (1:2) as the eluent, yielding 7.65 g (17.8 mmol, 70 %). 1H NMR (400 MHz, CDCl3): δ 9.88 (s, CHO), 7.83 (d, J = 8.8 Hz, 2H, Ar−H), 6.99 (d, J = 8.8 Hz, 2H, Ar−H), 4.04 (t, J = 6.6 Hz, 2H, OCH2), 1.81 (quin, J = 5.7 Hz, 2H, OCH2CH2), 1.25 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.3 Hz, 3H, CH3). Third step (preparation of 4-n-docosyloxystilbenecarboxylic acid): From (4-methoxycarbonylbenzyl)triphenylphosphonium bromide (8.76 g, 17.8 mmol) and 4-docosyloxybenzaldehyde (7.65 g, 17.8 mmol), recrystallized twice from acetic acid, yielding 2.38 g (4.34 mmol, 24%). 1H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 8.7 Hz, 2H, Ar−H), 7.54 (d, J = 8.7 Hz, 2H, Ar−H), 7.45 (d, J = 8.7 Hz, 2H, Ar−H), 7.17 (d, J = 14.7 Hz, 1H, −CH=), 6.98 (d, J = 18.0 Hz, 1H, −CH=), 6.89 (d, J = 8.7 Hz, 2H, Ar−H), 3.99 (t, J = 6.4 Hz, 2H, OCH2), 1.79 (quin, J = 9.3 Hz, 2H, OCH2CH2), 1.26 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.4 Hz, 3H, CH3). Fourth step (1,2-Bis(4-n-docosyloxystilbenecarbonyl)hydrazine): From 4-n-docosyloxystilbenecarboxylic acid (1.00 g, 1.82 mmol), recrystallized from pyridine seven times, washed with THF, yielding 0.44 g (0.40 mmol, 43%). 1H NMR (400 MHz, pyridine-d5): δ 8.23 (d, J = 8.7 Hz, 4H, Ar−H), 7.59 (d, J = 8.3 Hz, 4H, Ar−H), 7.55 (d, J = 8.7 Hz, 4H, Ar−H), 7.27 (d, J = 16.0 Hz, 2H, −CH=), 7.10 (d, J = 16.5 Hz, 2H, −CH=), 7.02 (d, J = 10.6 Hz, 4H, Ar−H), 4.02 (t, J = 6.6 Hz, 4H, OCH2), 1.78 (quin, J = 6.5 Hz, 4H, OCH2CH2), 1.31 (m, 76H, OCH2CH2(CH2)19), 0.87 (t, J = 6.9 Hz, 3H, CH3). Elemental Anal. Calcd for C74H112N2O4: C, 81.25; H, 10.34; N, 2.56. Found: C, 80.90; H, 10.52; N, 2.61 %.

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4a. 1,2-Bis(4-n-octadecyloxyphenylethynylbenzoyl)hydrazine (PEB-18) First step (preparation of 4-iodophenyloctadecylether):S4 4-iodophenol (4.30 g, 19.5 mmol), 1-bromo-n-octadecane (12.88 g, 38.6 mmol), and K2CO3 (8.12 g, 58.8 mmol) were dissolved in acetone (200 mL), and refluxed at 60-70 C for 42 h. After cooled, residual K2CO3 was filtered off, and from the filtrate, the solvent was removed with a rotary evaporator to give a brownish white solid. The crude product was twice recrystallized from ethanol, dried in vacuum, identified by 1H NMR. Yield 7.60 g (16.1 mmol), 83 %. 1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 9.3 Hz, 2H, Ar-H), 6.67 (d, J = 8.8 Hz, 2H, Ar−H), 3.90 (t, J = 6.6 Hz, 2H, OCH2), 1.76 (quin, J = 7.1 Hz, 2H, OCH2CH2), 1.45-1.20 (m, 30H, OCH2CH2(CH2)15), 0.88 (t, J = 6.8 Hz, 3H, CH3). Second step (preparation of (4-(trimethylsilylacetyl)phenoloctadecylether):S4 4-iodophenyloctadecylether (7.60 g, 16.1 mmol), trimethylsilylacetylene (5.28 g, 53.8 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.19 g, 0.27 mmol), Cu(I)I (0.087 g, 0.46 mmol), and triphenylphosphine (0.18 g, 0.67 mmol) were dissolved in trimethylamine (100 mL), and stirred at 40-60 C for 42 h under N2 atmosphere. After that, the residue was filtered off, and from the filtrate, the solvent was removed with a rotary evaporator to give a black solution. The solution was mixed with diethylether, washed twice with 1N HCl (100 mL), from which the aqueous layer was removed. The organic layer was diluted with a large amount of water to neutralize. The organic layer separated was dried with MgSO4 (10 g) and after filtration, the solvent was removed with a rotary evaporator to give a brownish white solid. The obtained product was recrystallized from ethanol (200 mL), dried in vacuum, identified by 1H NMR. Yield 5.80 g (13.1 mmol), 81 %. 1H NMR (400 MHz, CDCl3, r.t.): δ 7.42 (d, J = 8.8 Hz, 2H, Ar−H), 7.01 (d, J = 8.3 Hz, 2H, Ar−H), 4.01 (t, J = 6.8 Hz, 2H, OCH2), 1.77 (m, 2H, OCH2CH2), 1.44-1.23 (m, 30H, OCH2CH2(CH2)15), 0.89 (t, J = 6.8 Hz, 3H, CH3), 0.21 (m, 9H, Si-(CH3)3). Third step (preparation of 4-acetylphenyloctadecylether):S4 To 4-(trimethylsilylacetyl)phenyloctadecylether (5.80 g, 13.1 mmol) was slowly added NaOH (4.80 g, 120 mmol) dissolved in methanol-water (4:3) (350 mL) under dark. After the mixture was stirred for 24 h, diethylether (200mL) was added. The extracted organic layer was washed twice with 1N HCl (100 mL) and after that, diluted with a large amount of water. The obtained organic layer was dried with MgSO4 (10 g). After removing the MgSO4, the solvent was removed with a rotary evaporator. The resulting brownish oil was mixed with ethanol (200 mL), and the product was twice recrystallized from the hot

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solution, dried in vacuum, identified by 1H NMR. Yield 1.45 g (3.9 mmol), 30 %. 1H NMR (400 MHz, CDCl3): δ 7.41 (d, J = 8.8 Hz, 2H, Ar−H), 6.82 (d, J = 8.3 Hz, 2H, Ar−H), 3.95 (t, J = 6.6 Hz, 2H, OCH2), 2.99 (s, CH, 1H), 1.77 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.45-1.26 (m, 30H, OCH2CH2(CH2)15), 0.88 (t, J = 6.8 Hz, 3H, CH3). Fourth step (preparation of 1,2-bis(4-iodobenzoyl)hydrazine):S2 A mixture of 4-iodobenzoic acid (5.04 g, 20.3 mmol) and thionyl chloride (30 mL) was refluxed at 80 C under N2 atmosphere for 3.5 h. After cooled to room temperature, the remaining thionyl chloride was removed thoroughly under a reduced pressure. The resulting yellow solution was mixed with dry CHCl3 (100 mL). After confirming neutrality of the solution, hydrazine monohydrate (1.13 g, 22.6 mmol) was added dropwise under N2 atmosphere. After stirring at 60 C for 1 h, the precipitate was collected, washed with water and THF, and then recrystallized from DMF three times and from THF, dried in vacuum to give 1.96 (3.98 mmol, 20 %) of white crystalline solid. 1H NMR (400 MHz, DMSO-d6): δ 10.48 (s, 2H, CONH), 7.90 (d, J = 7.8 Hz, 4H, Ar−H), 7.69 (d, J = 7.8 Hz, 4H, Ar−H). Fifth step (preparation of 1,2-bis(4-n-octadecyloxyphenylethynylbenzoyl)-hydrazine):S5 4-acetylphenyloctadecylether (1.45 g, 3.91 mmol), 1,2-bis(4-iodobenzoyl)hydrazine (0.97 g, 1.97 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.061 g, 0.087 mmol), triphenylphosphine (0.073 g, 0.28 mmol), and Cu(I)I (0.061 g, 3.2 mmol) were dissolved in a mixed solvent of DMF (50 mL) and triethylamine (100 mL), and refluxed at 80 C for 34 h under N2 atmosphere. After filtrating the solution, brownish yellow crystalline solid was obtained. The crude product was recrystallized from THF (200 mL) and pyridine (100 mL) several times, dried in vacuum, yielding 0.42 g (1.29 mmol, 11 % ) of a yellow crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.34 (s, 2H, CONH), 8.20 (d, J = 8.2 Hz, 4H, Ar−H), 7.62 (d, J = 8.2 Hz, 4H, Ar−H), 7.58 (d, J = 9.2 Hz, 4H, Ar−H), 7.00 (d, J = 8.7 Hz, 4H, Ar−H), 3.99 (t, J = 6.4 Hz, 4H, OCH2), 1.77 (quin, 4H, J = 7.0 Hz, OCH2CH2), 1.54-1.12 (m, 60H, OCH2CH2(CH2)15), 0.88 (t, J = 6.6 Hz, 3H, CH3). Elemental Anal. Calcd for C66H92N2O4: C, 81.10; H, 9.49; N, 2.87. Found: C, 80.99; H, 9.73; N, 2.85 %.

4b. 1,2-Bis(4-n-docosyloxyphenylethynylbenzoyl)hydrazine (PEB-22) First step (preparation of 4-iodophenyldocosylether):S4 From 4-iodophenol (5.78 g, 26.3 mmol) and 1-bromo-n-docosane (10.35 g, 26.6 mmol), yielding 10.67 g (20.1 mmol, 76 %). 1H NMR (400 MHz, CDCl3, r.t.): δ 7.53 (d, J = 8.8 Hz, 2H, Ar-H), 6.67 (d, J = 8.8 Hz, 2H, Ar−H), 3.91 (t, J = 6.6 Hz, 2H, OCH2), 1.76 (quin, J = 7.0 Hz, 2H, OCH2CH2),

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1.47-1.20 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.6 Hz, 3H, CH3). 2013/1/25 NMR Second step (preparation of (4-(trimethylsilylacetyl)phenoldocosylether):S4 From 4-iodophenyldocosylether (10.65 g, 20.1 mmol) and trimethylsilylacetylene (4.05 g, 41.2 mmol), yielding 9.10 g (18.2 mmol, 91 %) of a yellowish brown solid. 1H NMR (400 MHz, CDCl3): δ 7.38 (d, J = 8.8 Hz, 2H, Ar−H), 6.80 (d, J = 8.8 Hz, 2H, Ar−H), 3.94 (t, J = 6.6 Hz, 2H, OCH2), 1.76 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.50-1.20 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.8 Hz, 3H, CH3), 0.23 (m, 9H, Si-(CH3)3). Third step (preparation of 4-acetylphenyldocosylether):S4 From 4-(trimethylsilylacetyl)phenyldocosylether (9.10 g, 18.2 mmol), yielding 7.69 g (18.0 mmol, 99 %). 1H NMR (400 MHz, CDCl3): δ 7.41 (dd, J1 = 6.9 Hz, J2 = 2.3 Hz, 2H, Ar−H), 6.83 (d, J = 9.2 Hz, 2H, Ar−H), 3.95 (t, J = 6.6 Hz, 2H, OCH2), 2.99 (s, CH, 1H), 1.77 (quin, J = 7.6 Hz, 2H, OCH2CH2), 1.47-1.20 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 6.8 Hz, 3H, CH3). Fourth step (preparation of 1,2-bis(4-iodobenzoyl)hydrazine):S2 From 4-iodobenzoic acid (4.50 g, 18.1 mmol), yielding 1.70 g (3.46 mmol, 19 %) of a white crystalline solid. 1H NMR (400 MHz, DMF-d7): δ 10.11 (s, 2H, CONH), 7.89 (d, J = 8.3 Hz, 4H, Ar−H), 7.74 (d, J = 8.3 Hz, 4H, Ar−H). Fifth step (preparation of 1,2-bis(4-n-docosyloxyphenylethynylbenzoyl)hydrazine):S5 From 4-acetylphenyldocosylether (2.73 g, 6.40 mmol) and 1,2-bis(4-iodobenzoyl)-hydrazine (1.70 g, 3.46 mmol), washed with THF, recrystallized from boiled pyridine several times, yielding 1.40 g (1.29 mmol, 37 %) of a yellow crystalline solid. 1H NMR (400 MHz, pyridine-d5): δ 11.17 (s, 2H, CONH), 8.20 (d, J = 8.2 Hz, 4H, Ar−H), 7.62 (d, J = 8.2 Hz, 4H, Ar−H), 7.58 (d, J = 8.7 Hz, 4H, Ar−H), 7.00 (d, J = 8.7 Hz, 4H, Ar−H), 3.99 (t, J = 6.4 Hz, 4H, OCH2), 1.77 (quin, 4H, J = 7.0 Hz, OCH2CH2), 1.54-1.11 (m, 60H, OCH2CH2(CH2)19), 0.88 (t, J = 6.6 Hz, 3H, CH3). Elemental Anal. Calcd for C74H108N2O4: C, 81.57; H, 9.99; N, 2.57. Found: C, 81.85; H, 10.25; N, 2.62 %.

5a. N-(4-n-docosyloxybenzoyl)-N-(4-n-docosylnaphtoyl)hydrazine (B-N-12) First step (preparation of 4-n-dodecyloxybenzhydrazide):S6 Ethyl 4-n-dodecyloxybenzoate (1.60 g, 4.79 mmol) and hydrazine monohydrate (7.00 mL, 144 mmol) were dissolved in ethanol (20 mL) and refluxed at 80 C under N2 atmosphere for 6.5 h. After cooled to room temperature, gel-like precipitate was collected and recrystallized from ethanol, dried in vacuum, identified by 1H NMR. Yield 0.78 g (2.43 mmol), 51 %. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 8.7 Hz, 2H, Ar-H), 7.19 (s, 1H, NHNH2), 6.91 (d, J = 8.7 Hz, 2H, Ar-H), 4.05 (s, 2H, NHNH2), 3.98 (t, J = 6.6 Hz, 2H, OCH2), 1.78 (quin, J = 7.3 Hz, 2H, OCH2CH2), 1.49-1.20 (m, 18H, OCH2CH2(CH2)9), 0.87 (t, J = 6.9 Hz, 3H, CH3).

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Second step (preparation of N-(4-n-dodecyloxybenzoyl)-N-(4-n-dodecylnaphtoyl)hydrazine:S6 6-n-dodecyloxy-2-naphthoic acid (1.19 g, 3.34 mmol) was dissolved in dry toluene (20 mL), to which several drops of DMF and thionyl chloride (4.00 mL, 55.1 mmol) were added and refluxed at 80 C for 3.5 h under N2 atmosphere. After that, the solvent was removed under a reduced pressure. The obtained chloride was dissolved in dry toluene (20 mL), to which a solution of 4-n-dodecyloxybenzhydrazide (0.78 g, 2.43 mmol) and N,N-diisopropylethylamine (1.00mL, 5.75 mmol) dissolved in dry toluene (20 mL) was added slowly dropwise in 15 min and refluxed at 80 C for 30 min. After gradually cooled to room temperature, the solution was extracted into mixed solvents of toluene and water. The organic layer was dried with MgSO4 and the solvent was removed with a rotary evaporator. The obtained crude product was recrystallized twice from THF and once from acetone, and finally dried in vacuum, affording a yellowish white powder. Yield 0.10 g (0.15 mmol, 4.5 %). δ 9.28 (d, J = 6.9 Hz, 1H, NH), 9.15 (d, J = 6.9 Hz, 1H, NH), 8.32 (s, 1H, Ar-H), 7.85-7.77 (m, 5H, Ar-H), 7.22-7.19 (m, 1H, Ar-H), 7.15 (d, J = 2.3 Hz, 1H, Ar-H), 6.96 (d, J = 9.2 Hz, 2H, Ar-H), 4.09 (t, J = 7.1 Hz, 2H, OCH2), 4.01 (t, J = 6.4 Hz, 2H, OCH2), 1.83 (m, 4H, OCH2CH2), 1.50-1.20 (m, 36H, OCH2CH2(CH2)9), 0.88 (t, J = 6.6 Hz, 6H, CH3). Elemental Anal. Calcd for C42H62N2O4: C, 76.55; H, 9.48; N, 4.25. Found: C, 76.33; H, 9.71; N, 4.26 %. 5b. N-(4-n-docosyloxybenzoyl)-N-(4-n-docosylnaphtoyl)hydrazine (B-N-22) First step (preparation of 4-n-docosyloxybenzhydrazide):S6 Ethyl 4-n-docosyloxybenzoate (1.43 g, 3.01 mmol) and hydrazine monohydrate (7.50 mL, 150 mmol) were dissolved in ethanol (20 mL) and refluxed at 80 C under N2 atmosphere for 23 h. After cooled to room temperature, gel-like precipitate was collected and recrystallized from ethanol, dried in vacuum, identified by 1H NMR. Yield 0.94 g (2.04 mmol), 68 %. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 9.2 Hz, 2H, Ar-H), 7.18 (s, 1H, NHNH2), 6.91 (d, J = 9.2 Hz, 2H, Ar-H), 4.05 (s, 2H, NHNH2), 3.98 (t, J = 6.7 Hz, 2H, OCH2), 1.78 (quin, J = 8.2 Hz, 2H, OCH2CH2), 1.48-1.13 (m, 38H, OCH2CH2(CH2)19), 0.86 (t, J = 7.1 Hz, 3H, CH3). Second step (preparation of N-(4-n-docosyloxybenzoyl)-N-(4-n-docosylnaphtoyl)hydrazine:S6 6-n-docosyloxy-2-naphthoic acid (1.00 g, 2.01 mmol) was dissolved in dry toluene (20 mL), to which several drops of DMF and thionyl chloride (0.18 mL, 2.55 mmol) were added and refluxed at 80 C for 2h under N2 atmosphere. After that, the solvent was removed under a reduced pressure. The obtained chloride was dissolved in dry toluene (20 mL), to which a solution of 4-n-docosyloxybenzhydrazide (0.94 g, 2.04 mmol) and N,N-diisopropylethylamine (1.00mL, 5.75 mmol) dissolved in dry toluene (20 mL) was added slowly dropwise in 5 min and

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refluxed at 80 C for 30 min. After gradually cooled to room temperature, the white precipitate was collected, recrystallized from toluene and washed twice with hot acetone, and finally dried in vacuum, affording a white crystalline solid. Yield 0.70 g (3.45 mmol, 37 %). δ 9.17 (d, J = 7.3 Hz, 1H, NH), 9.04 (d, J = 6.9 Hz, 1H, NH), 8.32 (s, 1H, Ar-H), 7.84-7.77 (m, 5H, Ar-H), 7.23-7.20 (m, 1H, Ar-H), 7.15 (d, J = 2.3 Hz, 1H, Ar-H), 6.96 (d, J = 8.7 Hz, 2H, Ar-H), 4.10 (t, J = 6.8 Hz, 2H, OCH2), 4.02 (t, J = 6.9 Hz, 2H, OCH2), 1.83 (m, 4H, OCH2CH2), 1.54-1.13 (m, 76H, OCH2CH2(CH2)19), 0.88 (t, J = 7.1 Hz, 6H, CH3). Elemental Anal. Calcd for C62H102N2O4: C, 79.26; H, 10.94; N, 2.98. Found: C, 79.39; H, 11.23; N, 3.07 %.

6a. N-(4-n-decyloxybenzoyl)-N-(4-n-decyloxyphenylbenzoyl)hydrazine (B-PB-10) First step (preparation of 4-n-decyloxybenzhydrazide):S6 Ethyl 4-n-decyloxybenzoate (2.55 g, 8.33 mmol) and hydrazine monohydrate (12.0 mL, 240 mmol) were dissolved in ethanol (40 mL) and refluxed at 80 C under N2 atmosphere for 19 h. After cooled to room temperature, gel-like precipitate was collected and recrystallized from ethanol, dried in vacuum, identified by 1H NMR. Yield 0.99 g (3.39 mmol), 41 %. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 8.7 Hz, 2H, Ar-H), 7.21 (s, 1H, NHNH2), 6.91 (d, J = 9.2 Hz, 2H, Ar-H), 4.06 (s, 2H, NHNH2), 3.98 (t, J = 6.4 Hz, 2H, OCH2), 1.78 (quin, J = 7.2 Hz, 2H, OCH2CH2), 1.44-1.26 (m, 14H, OCH2CH2(CH2)7), 0.87 (t, J = 6.9 Hz, 3H, CH3). Second step (preparation of N-(4-n-decyloxybenzoyl)-N-(4-n-decyloxyphenylbenzoyl)hydrazine:S6 4-n-decyloxybiphenyl-4-carboxylic acid (1.42 g, 4.01 mmol) was dissolved in dry toluene (20 mL), to which several drops of DMF and thionyl chloride (4.00 mL, 55.1 mmol) were added and refluxed at 70 C for 3h under N2 atmosphere. After that, the solvent was removed under a reduced pressure. The obtained chloride was dissolved in dry toluene (20 mL), to which a solution of 4-n-decyloxybenzhydrazide (0.99 g, 3.39 mmol) and N,N-diisopropylethylamine (2.00mL, 11.5 mmol) dissolved in dry toluene (20 mL) was added slowly dropwise in 30 min and refluxed at 70 C for 30 min. After gradually cooled to room temperature, the white precipitate was collected, recrystallized twice from toluene, washed with hot acetone, and finally dried in vacuum, affording the final product. Yield 1.46 g (2.32 mmol, 58 %). 1H NMR (400 MHz, CDCl3): δ 9.10 (d, J = 7.4 Hz, 1H, NH), 8.99 (d, J = 6.9 Hz, 1H, NH), 7.90 (d, J = 8.2 Hz, 2H, Ar-H), 7.83 (d, J = 8.7 Hz, 2H, Ar-H), 7.66 (d, J = 8.7 Hz, 2H, Ar-H), 7.55 (d, J = 8.7 Hz, 2H, Ar-H), 6.97 (t, J = 9.6 Hz, 4H, Ar-H), 4.01 (m, 4H, OCH2), 1.81 (quin, J = 7.0 Hz, 4H, OCH2CH2), 1.55-1.29 (m, 28H, OCH2CH2(CH2)7), 0.89 (t, J = 7.3 Hz, 6H, CH3). Elemental Anal.

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Calcd for C40H56N2O4: C, 79.26; H, 10.94; N, 2.98. Found: C, 79.39; H, 11.23; N, 3.07 %. 6b. N-(4-n-tetradecyloxybenzoyl)-N-(4-n-tetradecyoxyphenylbenzoyl)hydrazine (B-PB-14) B-PB-14 was prepared by the same procedure as described for B-PB-10. First step (preparation of 4-n-tetradecyloxybenzhydrazide):S6 From ethyl 4-n-tetradecyloxybenzoate (1.81 g, 7.48 mmol) and hydrazine monohydrate (8.00 mL, 165 mmol), recrystallized from ethanol and from hexane-ethyl acetate (1:1), yielding 0.44 g (1.26 mmol, 17 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 8.2 Hz, 2H, Ar-H), 7.19 (s, 1H, NHNH2), 6.91 (d, J = 9.2 Hz, 2H, Ar-H), 4.05 (s, 2H, NHNH2), 3.98 (t, J = 6.9 Hz, 2H, OCH2), 1.78 (quin, J = 8.2 Hz, 2H, OCH2CH2), 1.49-1.00 (m, 22H, OCH2CH2(CH2)11), 0.87 (t, J = 7.1 Hz, 3H, CH3). Second step (preparation of N-(4-n-tetradecyloxybenzoyl)-N-(4-n-tetradecyloxyphenylbenzoyl)hydrazine:S6 From 4-n-tetradecyloxybiphenyl-4-carboxylic acid (0.62 g, 1.51 mmol), thionyl chloride (2.00 mL, 27.7 mmol), and 4-n-tetradecyloxybenzhydrazide (0.43 g, 1.23 mmol), recrystallized five times from toluene and once from THF, yielding 0.59 g (0.80 mmol, 53 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 9.09 (d, J = 8.0 Hz, 1H, NH), 8.99 (d, J = 8.0 Hz, 1H, NH), 7.90 (d, J = 9.6 Hz, 2H, Ar-H), 7.82 (d, J = 8.7 Hz, 2H, Ar-H), 7.65 (d, J = 7.6 Hz, 2H, Ar-H), 7.54 (d, J = 9.2 Hz, 2H, Ar-H), 6.97 (t, J = 9.6 Hz, 4H, Ar-H), 4.02 (m, 4H, OCH2), 1.80 (quin, J = 7.6 Hz, 4H, OCH2CH2), 1.42-1.13 (m, 44H, OCH2CH2(CH2)11), 0.88 (t, J = 7.1 Hz, 6H, CH3). Elemental Anal. Calcd for C48H72N2O4: C, 77.79; H, 9.79; N, 3.78. Found: C, 77.69; H, 9.90; N, 3.97 %. 6c. N-(4-n-hexadecyloxybenzoyl)-N-(4-n-hexadecyoxyphenylbenzoyl)hydrazine (B-PB-16) B-PB-16 was prepared by the same procedure as described for B-PB-10. First step (preparation of 4-n-hexadecyloxybenzhydrazide):S6 From ethyl 4-n-hexadecyloxybenzoate (4.46 g, 11.4 mmol) and hydrazine monohydrate (10.0 mL, 206 mmol), recrystallized from ethanol and from hexane-ethyl acetate (1:1), yielding 1.69 g (4.48 mmol, 39 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 9.2 Hz, 2H, Ar-H), 7.13 (s, 1H, NHNH2), 6.91 (d, J = 6.9 Hz, 2H, Ar-H), 4.04 (s, 2H, NHNH2), 3.99 (t, J = 6.6 Hz, 2H, OCH2), 1.78 (quin, J = 7.6 Hz, 2H, OCH2CH2), 1.40-1.02 (m, 26H, OCH2CH2(CH2)13), 0.88 (t, J = 7.1 Hz, 3H, CH3). Second step (preparation of N-(4-n-hexadecyloxybenzoyl)-N-(4-n-hexadecyloxyphenylbenzoyl)hydrazine:S6 From 4-n-hexadecyloxybiphenyl-4-carboxylic acid (0.71 g, 1.62 mmol), thionyl chloride (0.12 mL, 1.65 mmol), and 4-n-hexadecyloxybenzhydrazide (0.61 g, 1.62 mmol), recrystallized five times from toluene, washed twice with THF and once with acetone, yielding 0.87 g (1.09 mmol, 67 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 9.09 (d, J = 7.0

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Hz, 1H, NH), 8.98 (d, J = 7.0 Hz, 1H, NH), 7.90 (d, J = 8.4 Hz, 2H, Ar-H), 7.82 (d, J = 9.2 Hz, 2H, Ar-H), 7.66 (d, J = 8.4 Hz, 2H, Ar-H), 7.55 (d, J = 9.2 Hz, 2H, Ar-H), 6.97 (t, J = 9.2 Hz, 4H, Ar-H), 4.01 (m, 4H, OCH2), 1.80 (quin, J = 7.3 Hz, 4H, OCH2CH2), 1.41-1.19 (m, 52H, OCH2CH2(CH2)13), 0.88 (t, J = 7.1 Hz, 6H, CH3). Elemental Anal. Calcd for C52H80N2O4: C, 78.34; H, 10.12; N, 3.51. Found: C, 78.23; H, 10.34; N, 3.58 %. 6d. N-(4-n-octadecyloxybenzoyl)-N-(4-n-octadecyoxyphenylbenzoyl)hydrazine (B-PB-18) B-PB-18 was prepared by the same procedure as described for B-PB-10. First step (preparation of 4-n-octadecyloxybenzhydrazide):S6 From ethyl 4-n-octadecyloxybenzoate (5.49 g, 13 mmol) and hydrazine monohydrate (22.27 g, 445 mmol), recrystallized from chloroform, yielding 2.14 g (5.29 mmol, 40 %) of a whote crystalline solid. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 9.2 Hz, 2H, Ar-H), 7.18 (s, 1H, NHNH2), 6.91 (d, J = 8.7 Hz, 2H, Ar-H), 4.06 (s, 2H, NHNH2), 3.98 (t, J = 6.9 Hz, 2H, OCH2), 1.78 (quin, J = 7.2 Hz, 2H, OCH2CH2), 1.44-1.25 (m, 30H, OCH2CH2(CH2)15), 0.87 (t, J = 7.4 Hz, 3H, CH3). Second step (preparation of N-(4-n-octadecyloxybenzoyl)-N-(4-n-octadecyloxyphenylbenzoyl)hydrazine:S6 From 4-n-octadecyloxybiphenyl-4-carboxylic acid (1.15 g, 2.46 mmol), thionyl chloride (4.00 mL, 55.1 mmol), and 4-n-octadecyloxybenzhydrazide (1.01 g, 2.50 mmol), recrystallized five times from toluene, washed twice with acetone and once with THF, yielding 1.32 g (1.55 mmol, 63 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 9.06 (d, J = 7.0 Hz, 1H, NH), 8.98 (d, J = 8.4 Hz, 1H, NH), 7.90 (d, J = 8.4 Hz, 2H, Ar-H), 7.82 (d, J = 8.4 Hz, 2H, Ar-H), 7.65 (d, J = 8.4 Hz, 2H, Ar-H), 7.54 (d, J = 8.4 Hz, 2H, Ar-H), 6.97 (t, J = 9.1 Hz, 4H, Ar-H), 4.01 (m, 4H, OCH2), 1.80 (quin, J = 7.8 Hz, 4H, OCH2CH2), 1.47-1.26 (m, 60H, OCH2CH2(CH2)15), 0.88 (t, J = 6.9 Hz, 6H, CH3). Elemental Anal. Calcd for C56H88N2O4: C, 78.82; H, 10.40; N, 3.28. Found: C, 78.59; H, 10.52; N, 3.23 %. 6e. N-(4-n-eicosyloxybenzoyl)-N-(4-n-eicosyoxyphenylbenzoyl)hydrazine (B-PB-20) B-PB-20 was prepared by the same procedure as described for B-PB-10. First step (preparation of 4-n-eicosyloxybenzhydrazide):S6 From ethyl 4-n-eicosyloxybenzoate (1.53 g, 3.42 mmol) and hydrazine monohydrate (8.00 mL, 165 mmol), washed with water, recrystallized from ethanol, yielding 0.88 g (2.03 mmol, 59 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 6.9 Hz, 2H, Ar-H), 7.22 (s, 1H, NHNH2), 6.90 (d, J = 8 Hz, 2H, Ar-H), 4.05 (s, 2H, NHNH2), 3.97 (t, J = 6.9 Hz, 2H, OCH2), 1.78 (quin, J = 7.6 Hz, 2H, OCH2CH2), 1.44-1.24 (m, 34H, OCH2CH2(CH2)17), 0.86 (t, J = 7.1 Hz, 3H, CH3). Second step (preparation of N-(4-n-eicosyloxybenzoyl)-N-(4-n-

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eicosyloxyphenylbenzoyl)hydrazine:S6 From 4-n-eisosyloxybiphenyl-4-carboxylic acid (1.00 g, 2.02 mmol), thionyl chloride (0.15 mL, 2.12 mmol), and 4-n-eisosyloxybenzhydrazide (0.88 g, 2.02 mmol), recrystallized four times from toluene, washed twice with THF, yielding 0.59 g (0.65 mmol, 32 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 8.98 (d, J = 6.5 Hz, 1H, NH), 8.82 (d, J = 6.5 Hz, 1H, NH), 7.90 (d, J = 8.6 Hz, 2H, Ar-H), 7.83 (d, J = 8.6 Hz, 2H, Ar-H), 7.66 (d, J = 8.6 Hz, 2H, Ar-H), 7.55 (d, J = 9.2 Hz, 2H, Ar-H), 6.97 (t, J = 9.2 Hz, 4H, Ar-H), 4.02 (m, 4H, OCH2), 1.81 (quin, J = 7.8 Hz, 4H, OCH2CH2), 1.47-1.26 (m, 68H, OCH2CH2(CH2)17), 0.88 (t, J = 6.8 Hz, 6H, CH3). Elemental Anal. Calcd for C60H96N2O4: C, 79.24; H, 10.64; N, 3.08. Found: C, 79.30; H, 10.76; N, 3.13 %. 6f. N-(4-n-docosyloxybenzoyl)-N-(4-n-docosyloxyphenylbenzoyl)hydrazine (B-PB-22) B-PB-22 was prepared by the same procedure as described for B-PB-10. First step (preparation of 4-n-docosyloxybenzhydrazide):S6 From ethyl 4-n-docosyloxybenzoate (1.42 g, 2.99 mmol) and hydrazine monohydrate (7.28 g, 146 mmol), washed with water, recrystallized from ethanol, and dried in vacuum, yielding 1.14 g (2.48 mmol, 83 %) of a white crystalline solid. 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 9.2 Hz, 2H, Ar-H), 7.17 (s, 1H, NHNH2), 6.91 (d, J = 9.2 Hz, 2H, Ar-H), 4.05 (s, 2H, NHNH2), 3.98 (t, J = 6 Hz, 2H, OCH2), 1.78 (quin, J = 8.2 Hz, 2H, OCH2CH2), 1.44-1.24 (m, 38H, OCH2CH2(CH2)19), 0.87 (t, J = 7.1 Hz, 3H, CH3). Second step (preparation of N-(4-n-docosyloxybenzoyl)-N-(4-n-docosyloxyphenylbenzoyl)hydrazine:S6 From 4-n-docosyloxybiphenyl-4-carboxylic acid (1.83 g, 3.51 mmol), thionyl chloride (0.25 mL, 3.50 mmol), and 4-n-docosyloxybenzhydrazide (1.61 g, 3.50 mmol), recrystallized three times from toluene, washed with THF, yielding 2.37 g (3.45 mmol, 70 %) of the final product. 1H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 8.4 Hz, 2H, Ar-H), 7.82 (d, J = 8.7 Hz, 2H, Ar-H), 7.66 (d, J = 8.7 Hz, 2H, Ar-H), 7.55 (d, J = 8.7 Hz, 2H, Ar-H), 6.97 (t, J = 9.2 Hz, 4H, Ar-H), 4.02 (m, 4H, OCH2), 1.82 (m, 4H, OCH2CH2), 1.4-1.16 (m, 76H, OCH2CH2(CH2)19), 0.88 (t, J = 7.1 Hz, 6H, CH3). Elemental Anal. Calcd for C64H104N2O4: C, 79.61; H, 10.88; N, 2.90. Found: C, 79.60; H, 11.10; N, 2.96 %. 7a. N-(4-n-docosyloxybenzoyl)-N-(4-n-docosyloxystilbenecarbonyl)hydrazine (B-S-22) First step (preparation of 4-n-docosyloxybenzhydrazide):S6 Same as described in 6f. Second step (preparation of N-(4-n-docosyloxybenzoyl)-N-(4-n-docosyloxystilbenecarbonyl)hydrazine:S6 4-n-decyloxystilbene-4-carboxylic acid (0.55 g, 1.00 mmol) was dissolved in dry toluene (20 mL), to which several drops of DMF and thionyl chloride (0.08 mL, 1.10 mmol) were

- 25 -

added and refluxed at 80 C for 1.5 h under N2 atmosphere. After that, the solvent was removed under a reduced pressure. The obtained chloride was dissolved in dry toluene (20 mL), to which a solution of 4-n-docosyloxybenzhydrazide (0.46 g, 1.00 mmol) and N,N-diisopropylethylamine (1.00mL, 5.75 mmol) dissolved in dry toluene (20 mL) was added slowly dropwise in 15 min and refluxed at 80 C for 30 min. After gently cooled to room temperature, the white precipitate was collected, recrystallized five times from toluene, washed with hot acetone, and finally dried in vacuum, affording the final product. Yield 0.68 g (0.68 mmol, 68 %). 1H NMR (400 MHz, pyridine-d5): δ 10.99 (s, 2H, NH), 8.22 (m, 4H, Ar−H), 7.58 (d, J = 8.3 Hz, 2H, Ar−H), 7.54 (d, J = 8.7 Hz, 2H, Ar−H), 7.27 (d, J = 16.0 Hz, 1H, −CH=), 7.10 (d, J = 16.5 Hz, 1H, −CH=), 7.03 (d, J = 8.7 Hz, 2H, Ar−H), 4.00 (m, 4H, OCH2), 1.77 (m, 4H, OCH2CH2), 1.54-1.14 (m, 78H, OCH2CH2(CH2)19), 0.88 (t, J = 6.6 Hz, 3H, CH3). Elemental Anal. Calcd for C66H106N2O4: C, 79.93; H, 10.80; N, 2.83. Found: C, 79.67; H, 11.13; N, 2.87 %.

8a. N-(4-n-docosyloxybenzoyl)-N-(4-n-docosyloxyphenylethynylbenzoyl)hydrazine (B-PEB-22) First step (preparation of 4-n-docosyloxyphenylethynylbenzoic acid):S4 4-acetylphenyldocosylether (1.98 g, 4.64 mmol), 4-iodobeonzoic acid (1.11 g, 4.48 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.485 g, 0.69 mmol), Cu(I)I (0.05 g, 0.26 mmol), and triphenylphosphine (0.07 g, 0.27 mmol) were dissolved in triethylamine (30 mL), and refluxed at 60 C for 20 h under N2 atmosphere. After cooled to room temperature, a yellow slurry precipitate was collected and washed with acetone, affording a white crystalline solid. The crude product was recrystallized from toluene, washed with hot acetone, dried in vacuum, identified by 1H NMR. Yield 1.78 g (3.26 mmol), 70 %. 1H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 9.2 Hz, 2H, Ar-H), 7.56 (d, J = 9.2 Hz, 2H, Ar-H), 7.46 (d, J = 9.2 Hz, 2H, Ar-H), 6.87 (d, J = 9.2 Hz, 2H, Ar-H), 3.97 (t, J = 6.9 Hz, 2H, OCH2), 1.78 (quin, J = 8.3 Hz, 2H, OCH2CH2), 1.47-1.26 (m, 38H, OCH2CH2(CH2)19), 0.88 (t, J = 7.3 Hz, 3H, CH3). Second step (preparation of N-(4-n-docosyloxybenzoyl)-N-(4-n-docosyloxyphenylethynylbenzoyl)hydrazine:S6 4-n-docosyloxyphenylethynyl-4-benzoic acid (1.02 g, 1.87 mmol) was dissolved in dry toluene (20 mL), to which several drops of DMF and thionyl chloride (0.13 mL, 1.90 mmol) were added and refluxed at 80 C for 1.5 h under N2 atmosphere. After that, the solvent was removed under a reduced pressure. The obtained chloride was dissolved in dry toluene (20 mL), to which a solution of 4-n-docosyloxybenzhydrazide (0.82 g, 1.78 mmol) (prepared as described in 6f) and N,N-diisopropylethylamine (1.00 mL, 5.75 mmol) dissolved in dry toluene (20 mL) was added slowly dropwise in 30 min and

- 26 -

refluxed at 80 C for 30 min. After gently cooled to room temperature, the white precipitate was collected, recrystallized three times from toluene, washed twice with hot acetone and twice with hot THF, and finally dried in vacuum, affording the final product. Yield 1.05 g (1.06 mmol, 57 %). 1H NMR (400 MHz, CDCl3): δ 9.05 (d, J = 8.8 Hz, 1H, NH), 8.93 (d, J = 7.2 Hz, 1H, NH), 7.82 (m, 4H, Ar-H), 7.59 (d, J = 8.7 Hz, 2H, Ar-H), 7.45 (d, J = 8.0 Hz, 2H, Ar-H), 6.94 (d, J = 8.8 Hz, 2H, Ar-H), 6.87 (d, J = 9.2 Hz, 2H, Ar-H), 4.00 (m, 4H, OCH2), 1.78 (m, 4H, OCH2CH2), 1.47-1.26 (m, 76H, OCH2CH2(CH2)19), 0.88 (t, J = 7.1 Hz, 6H, CH3). Elemental Anal. Calcd for C66H104N2O4: C, 80.11; H, 10.59; N, 2.83. Found: C, 79.99; H, 10.88; N, 2.91 %.

9a. 1,2-Bis[(4-n-docosyloxyphenyl)benzylidene]hydrazine (PBID-22) First step (4-n-docosyloxyphenylbenzylalchol): Ethyl 4-n-docosyloxyphenyl-4-beozoate (2.19 g, 3.98 mmol) was dissolved in dry THF (130 mL), to which diisobutylaluminium hydride (DIBAL) (19.5 mL) was added dropwise and stirred at room temperature for 2.5 H. After confirming the completion of the reaction with TLC (hexane-ethyl acetate (9:1) as eluent), water (3.0 mL) and 15 vol% NaOH aqueous solution (10 mL) were added in this order slowly and stirred at room temperature for 30 min. After that, the solvent was removed under a reduced pressure. The solution was mixed with ethyl acetate (150 mL), washed with 3N HCl (50 mL), from which the organic layer was extracted. The procedure was repeated three times. The solutions were summed and the solvent was removed with a rotary evaporator. The obtained white solid was dried at 60 C for 15 h, and finally identified by 1H NMR. Yield 1.94 g (3.82 mmol), 96 %. 1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 7.9 Hz, 2H, Ar-H), 7.49 (d, J = 9.0 Hz, 2H, Ar-H), 7.40 (d, J = 8.5 Hz, 2H, Ar-H), 6.95 (d, J = 8.5 Hz, 2H, Ar-H), 4.71 (d, J = 5.8 Hz, 2H, Ar-CH2OH), 3.99 (t, J = 6.1 Hz, 2H, OCH2), 1.79 (quin, J = 7.0 Hz, 2H, OCH2CH2), 1.76-1.26 (m, 38H, OCH2CH2(CH2)19), 0.87 (t, J = 6.5 Hz, 3H, CH3). Second step (4-n-docosyloxyphenylbenzylalchol): 4-n-docosyloxyphenylbenzylalchol (1.94 g, 3.82 mmol) was dissolved in toluene (140 mL), to which active MnO2 powder (1.95 g, 22.4 mmol) was added and refluxed at 80 C for 2.5 h. After confirming the completion of the reaction with TLC (hexane-ethyl acetate (9:1) as eluent), the residue was filtered off while hot. After that, the solvent was removed under a reduced pressure. The obtained white solid was washed with hot ethyl acetate and acetone, dried at 80 C for 24 h, and finally identified by 1H NMR. Yield 0.80 g (1.57 mmol), 41 %. 1H NMR (400 MHz, CDCl3): δ 10.02 (q, J = 7.0 Hz, 2H, Ar-CHO), 7.91 (d, J = 8.5 Hz, 2H, Ar-H), 7.70 (d, J = 6.7 Hz, 2H, Ar-H), 7.57 (d, J = 9.0 Hz, 2H, Ar-H), 6.98 (d, J = 8.5 Hz, 2H, Ar-H), 4.00 (t, J = 6.5 Hz, 2H, OCH2), 1.80 (m, 2H, OCH2CH2), 1.48-1.24 (m, 38H,

- 27 -

OCH2CH2(CH2)19), 0.87 (t, J = 7.0 Hz, 3H, CH3). Third step (preparation of 1,2-Bis[(4-n-docosyloxyphenyl)benzylidene]hydrazine: 4-n-docosyloxyphenylbenzaldehyde (0.75 g, 1.49 mmol) was dissolved in dry THF (20 mL), to which hydrazine monohydrate (0.036 mL, 0.72 mmol) was added dropwise and refluxed at 60 C for 2 h. After gently cooled to room temperature, the solvent was removed under a reduced pressure. The obtained yellowish white residue was recrystallized three times from toluene, washed with hot THF and with hot acetone, and finally dried at 60 C in vacuum for 25 h, affording the final product. Yield 0.09 g (0.09 mmol, 6 %). 1H NMR (400 MHz, pyridine-d5): δ 8.82 (s, 2H, -CH=N-), 8.02 (d, J = 8.5 Hz, 4H, Ar-H), 7.74 (d, J = 8.5 Hz, 4H, Ar-H), 7.68 (d, J = 9.0 Hz, 4H, Ar-H), 7.1 (overlapped with signals from hydrogenated pyridines, probably 4H, Ar-H), 4.04 (t, J = 6.7 Hz, 4H, OCH2), 1.80 (m, 4H, OCH2CH2), 1.52-1.33 (m, 76H, OCH2CH2(CH2)19), 0.86 (t, J = 7.3 Hz, 6H, CH3). Elemental Anal. Calcd for C70H108N2O4: C, 83.27; H, 10.78; N, 2.77. Found: C, 83.03; H, 10.98; N, 2.80 %.

- 28 -

2. DSC data 3.1. N-n series Figure S1. DSC heating thermograms at 5 K min-1 for N-n series. 3.2. PB-n series Figure S2. DSC heating thermograms at 5 K min-1 for PB-n series.

- 29 -

3.3. S-n series Figure S3. DSC heating thermograms at 5 K min-1 for S-n series. 3.4. PEB-n series

Figure S4. DSC heating thermograms at 5 K min-1 for PEB-n series.

- 30 -

Figure S5. Phase diagrams of five Cub-phase series containing symmetric molecular cores as a function of temperature (T) and the number of carbon atoms in the alkoxy chain (n); abbreviations: Sm = higher order smectic phase; SmC = smectic C phase; Ia3d = bicontinuous cubic phase with Ia3d symmetry; I432 = chiral cubic phase probably with I432 symmetry; Colh = hexagonal columnar phase.

- 31 -

3.5. B-N-n series

Figure S6. DSC heating thermograms at 5 K min-1 for B-N-n series.

3.6. B-PB-n series Figure S7. DSC thermograms on 3rd heating at 5 K min-1 for B-PB-n series.

- 32 -

3.7. B-S-22, B-PEB-22, and PBID-22

Figure S8. DSC thermograms at 5 K min-1 for B-S-22 and B-PEB-22 (both on 1st heating) and PBID-22 (on the 3rd heating).

- 33 -

4. X-ray data 4.1. XRD patterns of N-n series (1a) N-12

Figure S9. XRD patterns of N-12 on heating.

1 2 3 4 5 6

Inte

nsity

/ a.

u.

2

N-12at 483 KSmL=3.48 nm

(002

)

(001

)

× 10

- 34 -

(1b) N-16

1 2 3 4 5 6log

(Inte

nsity

/ a.

u.)

2

(321

)

(332

)

(400

) (420

)

(211

)(2

20)

(422

)(4

31)

N-16at 463 KIa3d-Cubbia=9.47 nm


1 2 3 4 5 6log

(Inte

nsity

/ a.

u.)

2

N-16at 448 KSmL=5.10 nm

(002

)

(003

)

(001

)

- 35 -

(1c) N-18


1 2 3 4 5 6

(001

)

(002

)

(003

)

(321

)(2

22)

(310

)

(400

)(4

11)

(420

)(4

22)

(431

)(5

21)

(721

)

Log(

Inte

nsity

/ a.

u.)

N-18Smat 433 KL=5.52 nm

Iso at 489 K

2

I432-Cub[*] at 456 K a=14.80 nm

I432-Cub[*] at 465 K

- 36 -

(1d) N-20

1 2 3 4

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)

(400

)

(332

)(4

22)

(431

)(321

)

× 200



1 2 3 4

Ia3d

-(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

Ia3d

-(211

)

Ia3d

-(420

)

Ia3d

-(400

)

Ia3d

-(332

)

Sm-(

001)

Sm-(

002)

Ia3d

-(321

)

× 200

Sm-(

003)

N-20at 446 KSm+Ia3d-Cubbi

L=5.89 nm

- 37 -

(1e) N-22

1 2 3 4

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)

(400

)

(332

)(4

22)

(431

)(321

)

× 200


Figure S13 XRD patterns of N-22 on heating.

1 2 3 4q / nm-1

N-22at 427 KSmL=5.81 nm

log(

Inte

nsity

/ a.

u.)

(001

)

(002

)

× 50(003

)

- 38 -

4.2. XRD patterns of PB-n series (2a) PB-10

1 2 3 4q / nm-1

PB-10at 510 KSmL=3.56 nm

log(

Inte

nsity

/ a.

u.)

(001

)

× 200

(002

)

Kap

ton

Figure S14. XRD patterns of PB-10 on heating.

- 39 -

(2b) PB-12

1 2 3 4q / nm-1

log(

Inte

nsity

/ a.

u.)

× 200

(001

)

(002

)

PB-12at 534 KSmL=3.75 nm

1 2 3 4q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

× 50

(220

)Sm

-(001

)

PB-12at 575 KIa3d-Cubbia=9.51 nm

- 40 -

(2c) PB-14

1 2 3 4q / nm-1

log(

Inte

nsity

/ a.

u.)

× 100

Sm-(0

01)

Sm-(0

02)

Ia3d

-(220

) Ia3d

-(321

)Ia

3d-(4

00)

Ia3d

-(420

)

PB-14at 505 KSm+Ia3d-Cubbi

L=4.03 nm

1 2 3 4

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)(400

)(3

21)

× 100


- 41 -

(2d) PB-16

1 2 3 4

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)(3

32)

(422

)(4

31)

(321

)

× 200


(400

)


- 42 -

(2e) PB-18


1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(400

)

(420

)(321

)

(220

)

(422

)(3

32)

(431

)


× 50

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)(4

11)

(400

)

(420

)

(222

)(3

10)

(422

)

(521

)

(431

)

× 30

PB-18at 563 KI432-Cub[*]a=16.21 nm

- 43 -

(2f) PB-19

Figure S19. XRD pattern of PB-19 on heating.

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)(4

11)

(400

)

(420

)

(222

)(3

10)

(422

)

(521

)

(431

)

× 50

PB-19at 485 KI432-Cub[*]a=17.03 nm

- 44 -

(2g) PB-20

1 2 3 4

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)

(400

)

(332

)(4

22)

(431

)

(321

)

× 200



1 2 3 4

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)

(411

)(4

00)

(222

)(3

10)

(422

)

(521

)

(721

)

(431

)

× 50

PB-20at 514 KI432-Cub[*]a=17.25 nm

(420

) (530

)

- 45 -

(2h) PB-21

1 2 3

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)(400

)

(332

)(4

22)

(431

)

× 100



1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)

(411

)(4

00)

(420

)

(310

)

(422

)

(521

)(510

)

× 50

(222

)PB-21at 495 KI432-Cub[*]a=17.73 nm

- 46 -

(2i) PB-22

1 2 3 4

log(

Inte

nsity

/ a.

u.)

q / nm-1

(100

) PB-22at 558 KColha=5.07 nm

(110

)

× 100

1 2 3 4

(220

)

q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(420

)

(400

) (332

)(4

22)

(431

)

× 200


(321

)


1 2 3 4

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)(4

11)

(420

)

(310

)

(422

)

(521

)(5

10)

× 100

(222

)

(721

)

(631

)

PB-22at 495 KI432-Cub[*]a=18.07 nm

(710

)

- 47 -

4.3. XRD patterns of S-n series (3a) S-16

1 2 3

log(

Inte

sity

/ a.

u. )

q / nm-1

(211

)

(220

)

(321

)(4

00)

(420

)

(431

)

S-16at 586.2 KIa3d-Cubbia=11.30 nm

Figure S23. XRD patterns of S-16 on heating.

1 2 3

log(

Inte

sity

/ a.

u. )

q / nm-1

(001

)

(002

)

S-16at 508 KSmL=4.40 nm

- 48 -

(3b) S-18

1 2 3q / nm-1

log(

Inte

sity

/ a.

u.)

(211

)

(220

)

(321

)(4

00)

(420

)

(521

)(4

22)

S-18at 557.0 KI3d-Cubbia=11.90 nm

Figure S24. XRD patterns of S-18 on heating. At 515.9 K, a peak that originated from the high-temperature Ia3d phase was detected at 1.25 nm-1 probably due to structural fluctuation, although the fraction was a trace amount (0.6%).

1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

) (310

) (22

2)(3

21)

(400

)(4

11)

(420

)(4

22)

(431

)(5

21)

S-18at 571.6 KI432-Cub[*]a=17.85 nm

1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

(001

)

(002

)

S-18at 515.9 KSmL=4.59 nm

Ia3d

-(21

1)

- 49 -

(3c) S-20


1 2 3log

(Inte

nsity

/ a.

u. )

q / nm-1

(211

) (310

) (222

)(3

21)

(400

)(4

11)

(420

)(4

22)

(431

)(5

21)

S-20at 515.9 KI432-Cub[*]a=19.12 nm

- 50 -

(3d) S-22

1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

(211

)

(220

)

(420

)(3

32)

(422

)(4

31)

(321

)

S-22at 580.4 KIa3d-Cubbia=12.04 nm

1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

(100

)

(110

)

S-22at 595.0 KColha=5.43 nm


1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

(321

)

(400

)

(222

)(3

10)

(211

)

(411

)(4

20)

(422

)(4

31)

(521

)

S-22at 571.6 KI432-Cub[*]a=18.99 nm

(433

)

(631

)(7

21),

(633

),(5

52)

(732

),(6

51)

- 51 -

4.4. XRD patterns of PEB series (4a) PEB-18

Figure S27. XRD patterns of PEB-18 on heating.

1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

(001

)

(002

)

× 100

PEB-18at 507 KSmL=4.48 nm

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)

(431

)

(411

)(4

20)

(211

)

(310

)

(422

)

(521

)

× 10

PEB-18at 556 KI432-Cub[*]a=17.72 nm

- 52 -

(4b) PEB-22

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(100

)

(110

)

× 200

PEB-22at 539 KColha=4.83 nm

Figure S28. XRD patterns of PEB-22 on heating.

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(321

)

(411

)(4

00)

(420

)

(310

)

(422

)

(521

)(4

31)

× 50

PEB-22at 495 KI432-Cub[*]a=19.55 nm

- 53 -

4.5. XRD patterns of B-N series (5a) B-N-12 (5b) B-N-22

Figure S29. XRD pattern of B-N-12 on heating.

1 2 3q / nm-1

log(

Inte

nsity

/ a.

u.)

B-N-22at 418.4 KIa3d-Cubbia=9.99 nm

(211

)

(220

)

(400

)(4

20)

(332

)(4

22)

(431

)

(321

)

Figure S30. XRD pattern of B-N-22 on heating.

1 2 3 4 5

log(

Inte

nsity

/ a.

u.)

q / nm-1

(001

)

(002

)

B-N-12at 433.4 KSmL=3.41 nm

- 54 -

4.6. XRD patterns of B-PB series (6a) B-PB-10 (6b) B-PB-14

Figure S31. XRD pattern of B-PB-10 on heating.

Figure S32. XRD pattern of B-PB-14 on heating.

10 20

log(

Inte

nsity

/ a.

u.)

2θ/ °

(001

)(0

02)

B-PB-14at 473.2 KSmL=3.79 nm

Kapton

10 20

log(

Inte

nsity

/ a.

u.)

2θ/ °

(001

)

B-PB-10at 473.2 KSmL=3.24 nm

Kapton

- 55 -

(6c) B-PB-16

Figure S33. XRD patterns of B-PB-16 on heating.

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(220

)

(400

)

(332

)(4

22)

(431

)

B-PB-16at 486.5 KIa3d-Cubbia=9.71 nm

(321

)

10 20

log(

Inte

nsity

/ a.

u.)

2θ/ °

(001

)(0

02)

B-PB-16at 450.2 KSmL=4.08 nm

Kapton

- 56 -

(6d) B-PB-18


10 20

log(

Inte

nsity

/ a.

u.)

2θ/ °

(001

)(0

02)

B-PB-18at 433.2 KSmL=4.34 nm

(003

)Kapton

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(521

)

(400

)

(420

)

(310

)

(422

)(4

31)

B-PB-18at 472.5 KI432-Cub[*]a=15.38 nm

(222

)(3

21)

(411

)

- 57 -

(6e) B-PB-20

1 2 3 4 5

log(

Inte

nsity

/ a.

u.)

(220

)

(210

) B-PB-20at 493.2 KIa3d-Cubbia=10.18 nm

2θ/ °

(332

)

(420

)


10 20

log(

Inte

nsity

/ a.

u.)

2θ/ °

(001

)(0

02)

B-PB-20at 418.2 KSmL=4.63 nm

(003

)

1 2 3 4 5

log(

Inte

nsity

/ a.

u.)

(222

)(3

10)

B-PB-20at 448.2 KI432-Cub[*]a=16.40 nm

2θ/ °

(321

)

(400

)(4

11)

(420

)(4

22)

(431

)(5

21)

- 58 -

(6f) B-PB-22


1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(220

)

(400

)(4

20)

(332

)(4

22)

(431

)

B-PB-22at 464.9 KIa3d-Cubbia=10.58 nm

(321

)

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(521

)

(400

)

(420

)

(310

)

(422

)(4

31)

B-PB-22at 425.4 KI432-Cub[*]a=17.17 nm

(222

)(3

21)

(411

)

- 59 -

4.7. XRD patterns of B-S-22

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(220

)

(400

)(4

20)

(332

)(4

22)

(431

)

B-S-22at 493.0 KIa3d-Cubbia=11.67 nm

(321

)

Figure S37. XRD patterns of B-S-22 on heating.

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(521

)

(400

)

(420

)

(310

)

(422

)(4

31)

B-S-22at 445.3 KI432-Cub[*]a=18.16 nm

(222

)(3

21)

(411

)

- 60 -

4.8. XRD patterns of B-PEB-22

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(220

)

(400

)(4

20) (3

32)

(422

)(4

31)

B-PEB-22at 483.7 KIa3d-Cubbia=11.05 nm

(321

)

Figure S38. XRD pattern of B-PEB-22 on heating.

1 2 3

log(

Inte

nsity

/ a.

u.)

q / nm-1

(211

)

(521

)

(400

)

(420

)

(310

)

(422

)(4

31)

B-PEB-22at 445.3 KI432-Cub[*]a=18.11 nm

(222

)(3

21)

(411

)

- 61 -

4.9. XRD patterns of PBID-22

Figure S39. XRD patterns of PBID-22 on heating. Three different smectic phases are designated Sm1 to Sm3 having different layer thicknesses L’s.

- 62 -

5. POM (1c) N-18

(3c) S-20

Figure S40. POM images for the I432 phase of N-18 on heating, observed under crossed polarizers (b) and under slightly uncrossed analyzer (A), +10º (a) and −10º (c), out of the complete 90º position with respect to the polarizer (P).

Figure S41. POM images for the I432 phase of S-20 at 503 K

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Supporting Information · 2018. 1. 31. · - 1 - Supporting Information Systematic exploitation of thermotropic bicontinuous cubic phase families from 1,2-bis(aryloyl)hydrazine-based