1G (bottom) with the phase-transition temperatures in C and associated enthalpy changes (in

Transcription

1 Supplementary Figure 1. Optical properties of 1 in various solvents. UV/Vis (left axis) and fluorescence spectra (right axis, ex = 420 nm) of 1 in hexane (blue lines), toluene (green lines), THF (yellow lines), CH 2 Cl 2 (orange lines) and CH 3 CN (red lines). Concentrations of the solutions for UV measurements are M. Supplementary Figure 2. POM and DSC analysis of 1G # and 1G. (a) POM images of 1G # (upper) and 1G (bottom). Scale bar: 100 m in all the images. (b) DSC traces of 1G # (upper) and 1G (bottom) with the phase-transition temperatures in C and associated enthalpy changes (in brackets) in kcal mol 1.

2 Supplementary Figure 3. PXRD patterns of 1G # and 1G. PXRD patterns of 1G # (upper) and 1G (bottom). Supplementary Figure 4. UV/Vis spectra of 1G # and 1G. UV/Vis spectra of 1G # (black dashed line) and 1G (green line).

3 Supplementary Figure 5. Crystal structure of 2. (a) Optical (upper) and fluorescence micrographs (lower) of orange-emitting single crystals of 2 obtained from ethyl acetate. Scale bar: 1 mm. (b) Lamellar packing arrangement (ORTEP drawing) of X-ray crystal structure of 2. Crystallographic axes b and c are indicated by arrows. Supplementary Figure 6. Fluorescence spectra of 1G # and 1G. Fluorescence spectra of 1Y (yellow line), 1O (orange line), 1G # (green line) and 1G (blue line). ex = 400 nm.

4 Supplementary Figure 7. PXRD pattern of 1O Li. PXRD pattern of 1O Li prepared by immersing 1O in aqueous acetonitrile solution of CF 3 SO 3 Li (10 wt%). The diffractions of remaining 1O are also observed. Supplementary Figure 8. Inkjet fluorescence imaging using 1. Inkjet writing of a cartoon picture of an orange fruit and the characters ORANGE (ca. 1 cm in size) on 1O by using 10 wt% water-acetonitrile solution of CF 3 SO 3 Li. (a) Photographs of the inkjetted sample using solution under room light (left) and under UV light (right). (b) Left: photographs of the inkjetted sample under UV after 1G # -seeding. Right: fluorescent microscopic image of a part of the letter E (scale bar: 0.5 mm).

5 R 1 N R 1 i) R 1 R 1 N ii) R 1 R 1 N CHO CN CHO 3a: R 1 = (CH 2 ) 11 CH 3 3b: R 1 = (CH 2 ) 5 CH 3 4a: R 1 = (CH 2 ) 11 CH 3 4b: R 1 = (CH 2 ) 5 CH 3 5a: R1 = (CH 2 ) 11CH 3 5b: R 1 = (CH 2 ) 5 CH 3 H 3 C(H 2 C) 11 (CH 2 ) 11 CH 3 N 5a iii) O OR 2 6a: R 2 iv) v) = CH 3 7a: R 2 = H 1: R 2 = (CH 2 CH 2 O) 3 CH 3 H 3 C(H 2 C) 5 (CH 2 ) 5 CH 3 N 5b iii) 2 O OCH 3 Supplementary Figure 9. Synthetic procedure of 1 and 2. i) Lithium diisopropylamide (LDA), diethyl 4-cyanobenzylphosphonate, tetrahydrofuran (THF), 78 C r.t.; ii) diisobutylaluminium hydride (DIBAL), ether, 78 C r.t.; iii) t-buok, methyl 4-((diethoxyphosphoryl)methyl)benzoate, THF, reflux; iv) KOH, EtOH, 70 C; v) triethylene glycol monomethyl ether, N,N-dimethyl-4-aminopyridine (DMAP), N,N-diisopropylethylamine (DIPEA), 4-(dimethylamino)-prydinium-4-toluenesulfonate (DPTS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), CH 2 Cl 2, 0 C r.t..

6 Supplementary Figure H-NMR chart of 1. Supplementary Figure C-NMR chart of 1.

7 Supplementary Figure H-NMR chart of 2. Supplementary Figure C-NMR chart of 2.

8 Supplementary Figure 14. ESI-MS spectra of 1. Supplementary Figure 15. ESI-MS spectra of 2.

9 Supplementary Table 1. Emission properties of 1 in solution state. Emission maximum wavelength ( em-max ), fluorescence quantum yield ( F ), average lifetime ( F ), and radiative rate constant (k F ) for each solution of 1. solvent em-max F F k F [nm] [-] [ns] a) [s -1 ] hexane toluene chloroform tetrahydrofuran dichloromethane acetonitrile a) Intensity-weighted mean Supplementary Table 2. Emission properties of 1 in the solid state. Emission maximum wavelength ( em-max ), fluorescence quantum yield ( F ), average lifetime ( av ), and radiative rate constant (k F ) for 1Y, 1O, 1G # and 1G. phase em-max F av k F [nm] [-] ns a [s -1 ] 1Y O G # G a) Intensity-weighted mean

10 Supplementary Table 3. Summary of X-ray crystallographic data for 2. Compound 2 CCDC Name CCDC Empirical Formula C 36 H 45 NO 2 Formula Weight Crystal System triclinic Crystal Size / mm a / Å (2) b / Å (2) c / Å (3) / (3) / (3) / (3) V / Å (6) Space Group P-1 (#2) Z value 4 Dcalc / g cm Temperature / K max / 54.9 (MoK ) / cm No. of Reflections Measured Total : Unique : (R int = ) No. of Observations (All reflections) Residuals: R 1 (I > 2.00 (I)) Residuals: wr 2 (All reflections) Goodness of Fit Indicator (GOF) Maximum peak in Final Diff. Map / Å 3 Minimum peak in Final Diff. Map / Å e 0.20 e

11 Supplementary Methods (E)-4-(4-(dihexylamino)styryl)benzonitrile (4b): Compound 3b (1.3 g, 4.5 mmol) was dissolved in dry THF (15 ml) and stirred under N 2 atmosphere at 78 C. LDA (4.1 ml, 8.1 mmol) was added slowly and the mixture was stirred for 10 min at 78 C. After diethyl 4-cyanobenzylphosphonate (1.4 g, 5.4 mmol) was added, the reaction was stirred overnight at room temperature. The solvent was evaporated in vacuo, and the resulting residue was dissolved in CHCl 3 and washed with water several times. The organic layer was dried over Na 2 SO 4 and solvent was evaporated. The residue was purified by column chromatography over silica gel to give compound 4b as yellow solid (0.9 g, 51 %). 1 H-NMR (300 MHz, CDCl 3 ): 7.58 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.9 Hz, 2H), 7.14 (d, J = 16 Hz, 1H), 6.83 (d, J = 16 Hz, 1H), 6.62 (d, J = 8.8 Hz, 2H), 3.29 (t, J = 7.7 Hz, 4H), 1.59 (m, 4H), 1.32 (m, 12H), 0.90 (m, 6H); 13 C-NMR (125 MHz, CDCl 3 ):, 143.1, 132.8, 132.5, 128.5, 126.2, 123.3, 121.4, 119.6, 111.6, 109.1, 51.1, 31.8, 27.4, 26.9, 22.8, 14.2; HRMS (m/z): [MH] + calcd for C 27 H 37 N 2, ; found, (E)-4-(4-(dihexylamino)styryl)benzaldehyde (5b): Compound 4b (0.8 g, 2.2 mmol) was dissolved in dry ether (15 ml) and stirred under N 2 atmosphere at 78 C. DIBAL (4.4 ml, 4.4 mmol) was added slowly, and the mixture was stirred for 12 h at room temperature. The reaction was quenched by excess amount of 10% aqueous acetic acid. The mixture was diluted with CHCl 3, and washed with water several times. The organic layer was dried over Na 2 SO 4 and the solvent was evaporated. The residue was purified by column chromatography over silica gel to give compound 5b as yellow solid (0.6 g, 77 %). 1 H-NMR (300 MHz, CDCl 3 ): 9.95 (s, 1H), 7.83 (d, J = 8.2 Hz, 2H), 7.59 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.8 Hz, 2H), 7.20 (d, J = 16 Hz, 1H), 6.90 (d, J = 16 Hz, 1H), 6.63 (d, J = 8.9 Hz, 2H), 3.29 (t, J = 7.7 Hz, 4H), 1.59 (m, 4H), 1.32 (m, 12H), 0.91 (t, J = 6.7 Hz 6H); 13 C-NMR (125 MHz, CDCl 3 ): 191.7,, 144.9, 134.4, 132.7, 130.4, 128.5, 126.2, 123.6, 122.0, 111.6, 51.1, 31.8, 27.4, 26.9, 22.8, 14.2; HRMS (m/z): [MH] + calcd for C 27 H 38 NO, ; found, Methyl 4-((E)-4-((E)-4-(dihexylamino)styryl)styryl)benzoate (2): Compound 5b (580 mg, 1.5 mmol), methyl 4-((diethoxyphosphoryl)methyl)benzoate (487 mg, 1.7 mmol) and t-buok (527 mg, 5.1 mmol) were mixed in dry THF (15 ml) and stirred under N 2 atmosphere. The mixture was refluxed for 3 h. After cooling, the solvent was evaporated. The residue was acidified with aq. HCl and extracted with CHCl 3. The organic layer was dried over Na 2 SO 4 and evaporated to dryness. The residue was purified by column chromatography over silica gel to give compound 2 as yellow solid

12 (233 mg, 30 %). 1 H-NMR (500 MHz, CDCl 3 ): 8.02 (d, J = 8.5 Hz, 2H), 7.57 (d, J = 8.4 Hz, 2H), 7.48 (m, 4H), 7.38 (d, J = 8.9 Hz, 2H), 7.21 (d, J = 16 Hz, 1H), 7.11 (d, J = 16 Hz, 1H), 7.07 (d, J = 16 Hz, 1H), 6.88 (d, J = 16 Hz, 1H), 6.62 (d, J = 9.0 Hz, 2H), 3.92 (s, 3H), 3.28 (t, J = 7.7 Hz, 4H), 1.59 (m, 4H), 1.33 (m, 12H), 0.91 (t, J = 6.8 Hz, 6H); 13 C-NMR (125 MHz, CDCl 3 ):.0, 148.0, 142.2, 138.6, 135.0, 131.2, 130.1, 129.4, 128.7, 128.0, 127.2, 126.7, 126.4, 126.3, 124.4, 123.1, 111.7, 52.2, 51.2, 31.8, 27.4, 26.9, 22.8, 14.2; HRMS (m/z): [MH] + calcd for C 36 H 46 NO 2, ; found, ((E)-4-((E)-4-(didodecylamino)styryl)styryl)benzoic acid (7a): Methyl 4-((diethoxyphosphoryl)methyl)benzoate (0.4 g, 1.4 mmol) and t-buok (0.3 g, 2.8 mmol) were mixed in dry THF (50 ml) and stirred under N 2 atmosphere. Compound 5a (0.6 g, 1.1 mmol) was added to the mixture and refluxed for 3 h. After cooling, KOH solution (10 ml, 6M in EtOH) was added to the mixture and stirred at 70 C for 3h. After cooling, the solvent was evaporated. The reactant was acidified with aq. HCl and extracted with CHCl 3. The organic layer was dried over Na 2 SO 4 and evaporated to dryness. The residue was purified by column chromatography over silica gel to give compound 7a as yellow solid (0.4 g, 58 %). 1 H-NMR (400 MHz, CDCl 3 ): 8.08 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 8.5 Hz, 2H), (m, 4H), 7.38 (d, J = 8.7 Hz, 2H), 7.28 (d, J = 16 Hz, 1H), 7.23 (d, J = 16 Hz, 1H), 7.12 (d, J = 16 Hz, 1H), 7.07 (d, J = 16 Hz, 1H), 6.88 (d, J = 16 Hz, 1H), 6.62 (d, J = 8.9 Hz, 2H), 3.27 (t, J = 7.0 Hz, 4H), (m, 4H), (m, 36H), 0.88 (t, J = 6.7 Hz, 6H). 13 C NMR spectrum of this compound could not be measured due to low solubility. This compound did not show mass peak in ESI- and APCI-MS measurements. 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-((E)-4-((E)-4-(didodecylamino)styryl)styryl)benzoate (1): Compound 7a (80 mg, 0.12 mmol) was dissolved in dry CH 2 Cl 2 (35 ml) and stirred under N 2 atmosphere at 0 C. Triethylene glycol monomethyl ether (20 mg, 0.12 mmol), DMAP (43 mg, 0.35 mmol), DIPEA (148 mg, 1.1 mmol), DPTS (104 mg, 0.35 mmol) and EDC (27 mg, 0.14 mmol) were added to the mixture. The solution was stirred overnight at room temperature. The reaction mixture was diluted with CHCl 3 and washed with water several times. The organic layer was dried over Na 2 SO 4 and the solvent was evaporated to dryness. The residue was purified by column chromatography over silica gel and reprecipitation (CHCl 3 / MeOH) to give compound 1 as yellow solid (77 mg, 80 %). 1 H-NMR (500 MHz, CDCl 3 ): 8.04 (d, J = 8.3 Hz, 2H), 7.56 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.6 Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 7.38 (d, J = 8.9 Hz, 2H), 7.21 (d, J = 16 Hz, 1H), 7.11 (d, J = 16 Hz, 1H), 7.07 (d, J = 16 Hz, 1H), 6.88 (d, J = 16 Hz, 1H), 6.62 (d, J = 8.9 Hz, 2H), 4.48 (t, J = 4.8 Hz, 2H), 3.85 (t, J = 4.8 Hz, 2H), (m, 8H), 3.38 (s, 3H), 3.28 (J, J =

13 7.7 Hz, 4H), (m, 4H), (m, 36H), 0.88 (t, J = 6.9 Hz, 6H); 13 C-NMR (125 MHz, CDCl 3 ): 166.5, 148.0, 142.2, 138.6, 135.0, 131.2, 130.2, 129.5, 128.7, 128.0, 127.2, 126.7, 126.3, 126.3, 124.4, 123.0, 111.7, 72.0, 70.8, 70.8, 70.7, 69.4, 64.2, 59.1, 51.2, 32.0, 29.8, 29.7, 29.6, 29.5, 27.4, 27.3, 22.8, 14.2; HRMS (m/z): [MNa] + calcd for C 54 H 81 NO 5 Na, ; found, ; Elemental analysis (calcd, found for C 54 H 81 NO 5 ): C (78.69, 78.55), H (9.91, 9.86), N (1.70, 1.86).