Supporting information for A Coordination Gelator that Shows a Reversible Chromatic Change and a Sol-Gel Phase Transition Behavior upon xidative / Reductive Stimuli Shin-ichiro Kawano, orifumi Fujita, and Seiji Shinkai* Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 6-10-1, akozaki, igashi-ku, Fukuoka 812-8581, Japan - Contents list- 1. Synthesis of 1, 2 p. S2 2. 1 MR spectra of 1, 2 p. S4,S5 3. T gel plot vs. [Cu(I)]/[1] p. S5 4. Various temperature-cd spectra of p. S6 Cu(I) 1 2 complex gel 5. Absorption and CD spectra p. S6 of reductively produced Cu(I) 1 2 complex gel 6. TEM image of reductively produced p. S7 Cu(I) 1 2 complex gel 7. Gelation properties of 1 and Cu(I) 1 2 complex p. S7 8. EPR spectra of the sol and the gel states of the Cu(I) 1 2 complex and UV spectra of the oxidized gel of the Cu(I) 1 2 complex p. S8 S1
1. Synthesis of 1, 2 2 C 2 C 2 2 Cl dry C 2 Cl 2 2 3 Cl * 2 C 2 C 2 2 dry C 2 Cl 2 2 * 4 C C SCl 2 ClC CCl 3 TEA dry C 2 Cl 2 R 1 C CR 1 1; Bip-Chol 5 R 1 = 4 TEA dry C 2 Cl 2 R 2 C CR 2 2; Bip-2-Etex R 2 = * Scheme S1 Materials All starting materials and solvents were purchased from Aldrich or Tokyo Kasei Chemicals and used as received. 3β- Cholest-5-en-3yl--(2-aminoethyl) carbamate (3) 1, 2-ethylhexyl-(2-aminoethyl)carbamate (4), and 2,2 -bipyridine-4,4 - diacidchloride (5) 2 were prepared according to the literature reported previously and identified by IR and 1 MR spectral S2
evidence. Synthesis of 1 3 (2.4 g, 5.1 mmol, 2.5 equiv) and triethylamine (1.2 ml, 8.6 mmol, 4.2 equiv) were dissolved in dry C 2 Cl 2 (50 ml) and cooled to 0 ºC. A dry C 2 Cl 2 solution of 5 (70 ml) was added dropwise during 1.5 hours. The reaction mixture was stirred for overnight at room temperature. The reaction mixture was washed with Cl aq. (0.1 mol dm -3 ) and saturated ac 3 aq., and then, twice with water and dried over a 2 S 4. The solvent was removed from the reaction mixture by evaporation and the residue was purified by column chromatography (Si 2 ; CCl 3 /C 3 = 30 /1) to afford 1 (0.97 g, 41%) as a colorless solid. Mp 227.2-227.4 ºC; 1 MR (600 Mz, TMS, CDCl 3 ) δ 0.67 (s, 6, C 3 ), 0.86-0.87 (m, 12, C 3 ), 0.91-2.34 (m. 68, C and C 2 ), 3.48-3.49 (m, 4, C 2 C), 3.63 (q, J = 5.3 z, 4, ArCC 2 ), 4.56 (sep, J = 5.0 z, 2, CC 2 ), 5.10 (br, 2, ArC), 5.28-5.29 (m, 2, C=C), 7.51 (br, 2, C), 7.78 (d, J = 4.3 z, 2, Ar), 8.75 (s, 2, Ar), 8.81 (d, J = 4.8 z, 2, Ar); MS (MALDI-TF, matrix; dithranol): 1154.55 [M + ] + ; 1153.83 calcd [M + ] + ; EA calcd for C 72 108 6 6 0.20CCl 3 : C 73.64, 9.26, 7.14; found C 73.57, 9.25, 7.21. Synthesis of 2 4 (0.78 g, 3.6 mmol, 2.2 equiv./ 5) and TEA (1.0 ml, 7.1 mmol, 4.3 equiv./ 5) were dissolved in dry C 2 Cl 2 (40 ml) and cooled to 0 ºC. A solution of 5 in dry C 2 Cl 2 (60 ml) was added dropwise during 2.0 hours. The reaction mixture was stirred from 0 ºC to room temperature for overnight. The mixture was washed with 0.1 -Cl aq., saturated ac 3 aq. and twice with water and dried over a 2 S 4. The solvent was removed by evaporation and the residue was purified by column chromatography (Si 2 ; CCl 3 /Me, 30 :1) to afford 1 (0.74 g, 70%) as a colorless solid. Mp 210.3-210.6 ºC; 1 -MR (600 Mz, TMS, CDCl 3 ) δ 0.84 (t, J = 5.5 z, 12, Me), 1.24-1.33 (m, 16, C 2 ), 1.52-1.53 (m. 2, C), 3.49-3.50 (m, 4, C 2 C), 3.64-3.66 (m, 4, ArCC 2 ), 3.99-4.04 (m, 4, CC 2 ), 5.17(br, 2, C), 7.45 (br, 2, ArC), 7.75 (d, J = 4.4 z, 2, Ar), 8.73 (s, 2, Ar), 8.78 (d, J = 4.6 z, 2, Ar); MS (MALDI-TF, matrix; dithranol): 641.39 calcd [M + ] +, found 642.08 [M + ] + ; EA: calcd for C 34 52 6 6 : C 63.73, 8.18, 13.11; found C 63.70, 8.17, 13.09. S3
2. 1 MR spectrum of 1 Figure S1. 600 Mz 1 MR spectrum of 1 in CDCl 3 S4
Figure S2. 600 Mz 1 MR spectrum of 2 in CDCl 3 3. T gel plot vs. [Cu(I)] /[1] (a) Tgel / ºC 180 160 140 Gel 120 Sol 100 80 60 40 0 5 10 15 20 25 [1] / g dm -3 (b) T gel / ºC 180 160 140 120 100 80 60 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 [Cu(I)] / [1] Figure S3. Plots of T gel vs. (a) [1], (b) [Cu(I)] / [1] in 1-PrC: (b) [1] = 6.1 mmol dm -3, [Cu(MeC) 4 PF 6 ] = 3.0 mmol dm -3. S5
4. Various temperature-cd spectra of Cu(I) 1 2 complex gel 10 5 CD / mdeg 0-5 -10-15 250 300 350 400 450 500 Wavelength / nm Figure S4. Various temperature-cd spectra of the gel of 1 + Cu(MeC) 4 PF 6 ; 1-PrC, [1] = 4.3 mmol dm -3, [Cu(MeC) 4 PF 6 ] = 2.2 mmol dm -3, 20 to 70 ºC. The contribution of LD (linear dichroism) was negligible under the same measurement conditions. 5. Absorption and CD spectra of reductively produced Cu(I) 1 2 complex gel (a) (b) Absorbance / a. u. Reduced Cu(I) gel Cu(I) gel CD / a. u. Cu(I) gel Reduced Cu(I) gel 400 500 600 700 800 Wavelength / nm 250 300 350 400 450 500 Wavelength / nm Figure S5. (a) Absorption and (b) CD spectra of the gel of 1 and a half molar equivalent of Cu(MeC) 4 PF 6 (the green line), the gel of 1, a half molar equivalent of Cu(Tf) 2 and about 1.6 molar equivalent of ascorbic acid (the blue line); 1-PrC, [1] = 8.7 mmoldm -3, 25 ºC. For the CD measurements, the contribution of LD was negligible under the same measurement conditions. S6
6. TEM image of reductively produced Cu(I) 12 complex gel 200 500nm nm Figure S6. TEM image of 1-PrC gels prepared from 1 (8.7 mmol dm-3) + Cu(Tf)2 (4.3 mmol dm-3) + ascorbic acid (6.9 mmol dm-3); stained with phosphotungstic acid aqueous solution (20 g dm-3). 7. Gelation properties of 1 and Cu(I) 12 complex Table S1. Gelation properties of 1, [Cu(1) 2]+ complex and [Cu(2)2]+ complex at 25 ºC. a Stateb Solvent 1 I Acetonitrile 1 + Cu(I) I 1-PrC Benzonitrile G G G Gc The other solventsd Gc S a Concentration of [1 or 2] is 8.7 mmol dm-3 (10 g dm-3), [Cu(MeC) 4PF 6] = 4.3 mmol dm-3. b G: gel, PG: partial gel, P: precipitation, I: insoluble when heated. c Gel at [1] = 22 mmol dm-3 (25 g dm-3), [Cu(MeC) 4PF 6] = 11 mmol dm-3. dbenzene, toluene, p-xylene, C Cl, CCl, TF, 12 2 3 butanol, 2-propanol, 1-propanol, ethanol. S7
8. EPR spectra of the sol and the gel states of the Cu(I) 1 2 complex and UV spectra of the oxidized gel of the Cu(I) 1 2 complex (a) state 1 state 2 state 3 Cooling Δ BF 4, Δ AsA, Δ Sol Gel Sol EPR silent EPR silent EPR active Cu(I) Cu(I) Cu(II) (b) (c) (i) (ii) Absorbance / A.U. (i) (ii) 2600 2800 3000 3200 3400 3600 3800 400 500 600 700 800 B / G Wavelength / nm Figure S7. (a) Photographs of the chromatic change and phase transition behavior of 1-PrC gel of Cu(I) 1 2. Conditions: see the manuscript. (b) EPR spectra of (i) 1-PrC gel prepared from 1 + 0.5 equiv Cu(MeC) 4 PF 6, [1] = 8.7 mmol dm -3 in 1-PrC at 25 ºC and (ii) the precipitate prepared by oxidation of above 1-PrC gel of Cu(I) 1 2 with 1.6 equiv BF 4. (c) UV-Vis absorption spectra of (i) the 1-PrC gel prepared from 1 + 0.5 equiv Cu(MeC) 4 PF 6, [1] = 8.7 mmol dm -3 in 1-PrC at 25 ºC and (ii) the KBr pellet with the precipitate prepared from 1 + 0.5 equiv Cu(MeC) 4 PF 6, and 1.6 equiv BF 4, [1] = 8.7 mmol dm -3 in 1-PrC at 25 ºC. (1) Ishi-i, T.; Iguchi, R.; Snip, E.; Ikeda, M.; Shinkai, S. Langmuir 2001, 17, 5825-5833. (2) Garelli,.; Vierling, P. J. rg. Chem. 1992, 57, 3046-3051. S8